WO2012096023A1 - Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and application thereof - Google Patents
Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and application thereof Download PDFInfo
- Publication number
- WO2012096023A1 WO2012096023A1 PCT/JP2011/068184 JP2011068184W WO2012096023A1 WO 2012096023 A1 WO2012096023 A1 WO 2012096023A1 JP 2011068184 W JP2011068184 W JP 2011068184W WO 2012096023 A1 WO2012096023 A1 WO 2012096023A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- fuel cell
- group
- metal
- oxygen reduction
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/46—C-H or C-C activation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for producing a fuel cell electrode catalyst, a fuel cell electrode catalyst, and uses thereof.
- a polymer solid fuel cell is a type of fuel in which a polymer solid electrolyte is sandwiched between an anode and a cathode, fuel is supplied to the anode, oxygen or air is supplied to the cathode, and oxygen is reduced at the cathode to extract electricity. It is a battery. Hydrogen or methanol is mainly used as the fuel.
- a layer containing a catalyst (hereinafter referred to as “for fuel cell”) is provided on the cathode (air electrode) surface or anode (fuel electrode) surface of the fuel cell. Also referred to as “catalyst layer”).
- a noble metal is generally used, and noble metals such as platinum and palladium which are stable at a high potential and have high activity among the noble metals have been mainly used.
- noble metals are expensive and have limited resources, development of alternative catalysts has been required.
- the noble metal used for the cathode surface may be dissolved in an acidic atmosphere, and there is a problem that it is not suitable for applications that require long-term durability. Therefore, there has been a strong demand for the development of a catalyst that does not corrode in an acidic atmosphere, has excellent durability, and has a high oxygen reducing ability.
- base metal substitute catalysts base metal carbides, base metal oxides, base metal carbonitrides, chalcogen compounds and carbon catalysts that do not use any precious metal have been reported (for example, see Patent Documents 1 to 4). These materials are cheaper and have abundant resources than noble metal materials such as platinum.
- Patent Document 3 and Patent Document 4 exhibit high oxygen reduction catalytic activity, but have a problem that their stability under fuel cell operating conditions is very low.
- Nb and Ti oxycarbonitrides in Patent Document 5 and Patent Document 6 are particularly attracting attention because they can effectively exhibit the above performance.
- Patent Document 5 and Patent Document 6 have extremely high performance compared to conventional noble metal substitute catalysts, heat treatment at a high temperature of 1600 ° C. to 1800 ° C. is necessary in a part of the production process. (For example, Patent Document 5 Example 1 or Patent Document 6 Example 1).
- Patent Document 7 discloses a method for producing an electrode catalyst characterized by firing a mixed material of an oxide and a carbon material precursor, but an electrode catalyst having sufficient catalytic performance has not been obtained. .
- Patent Document 8 discloses a fuel cell electrode catalyst using a polynuclear complex such as cobalt.
- the raw material has high toxicity, is expensive, and does not have sufficient catalytic activity. .
- JP 2004-303664 A International Publication No. 07/072665 Pamphlet US Patent Application Publication No. 2004/0096728 JP 2005-19332 A International Publication No. 2009/031383 Pamphlet International Publication No. 2009/107518 Pamphlet JP 2009-255053 A JP 2008-258150 A
- the object of the present invention is to solve such problems in the prior art.
- an object of the present invention is a high catalyst containing a metal element selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten and cerium after heat treatment at a relatively low temperature. It is an object of the present invention to provide a method for producing an active fuel cell electrode catalyst.
- Another object of the present invention is to provide a novel heat-treated product useful as an electrode catalyst for a fuel cell.
- an object of the present invention is to provide a fuel cell electrode catalyst having high catalytic activity and its use (electrodes, etc.).
- the present invention relates to the following [1] to [16], for example.
- Including A part or all of the metal compound (1) is a compound containing a metal element M1 selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten and cerium as a metal element.
- the compound [3] is at least one selected from the group consisting of a boric acid derivative containing fluorine, a sulfonic acid derivative containing fluorine, and a phosphoric acid derivative containing fluorine [2]
- the manufacturing method of the electrode catalyst for fuel cells of description is at least one selected from the group consisting of a boric acid derivative containing fluorine, a sulfonic acid derivative containing fluorine, and a phosphoric acid derivative containing fluorine [2] The manufacturing method of the electrode catalyst for fuel cells of description.
- the metal compound (1) is a metal phosphate, metal sulfate, metal nitrate, metal organic acid salt, metal acid halide, metal alkoxide, metal halide, metal perhalogenate, metal hypohalite and The method for producing an electrode catalyst for a fuel cell according to any one of the above [1] to [5], wherein the method is at least one selected from the group consisting of metal complexes.
- the nitrogen-containing organic compound (2) is an amino group, nitrile group, imide group, imine group, nitro group, amide group, azide group, aziridine group, azo group, isocyanate group, isothiocyanate group, oxime group, diazo group, And any one of the above-mentioned [1] to [6], wherein the molecule has at least one selected from the group consisting of a pyrrole ring, a porphyrin ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring.
- the manufacturing method of the electrode catalyst for fuel cells of description is an amino group, nitrile group, imide group, imine group, nitro group, amide group, azide group, aziridine group, azo group, isocyanate group, isothiocyanate group, oxime group, diazo group, And any one of the above-mentioned [1] to [6], where
- the nitrogen-containing organic compound (2) has one or more kinds selected from a hydroxyl group, a carboxyl group, an aldehyde group, an acid halide group, a sulfo group, a phosphoric acid group, a ketone group, an ether group, and an ester group in the molecule.
- the solid residue is heat-treated in an atmosphere containing 0.01% by volume to 10% by volume of hydrogen gas.
- a fuel cell catalyst layer comprising the fuel cell electrode catalyst according to [10] above.
- An electrode comprising the fuel cell catalyst layer according to the above [11] and a porous support layer.
- a membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is an electrode according to the above [12] Membrane electrode assembly.
- a fuel cell comprising the membrane electrode assembly according to the above [13].
- an electrode catalyst for a fuel cell of the present invention it is selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten, and cerium after heat treatment at a relatively low temperature. It is possible to produce an electrode catalyst for a fuel cell having a high catalytic activity and containing a metal element.
- the heat-treated product of the present invention is useful as a fuel cell electrode catalyst.
- the fuel cell electrode catalyst of the present invention has high catalytic activity and is useful for various applications (electrodes, etc.).
- FIG. 1 is a powder X-ray diffraction spectrum of the catalyst (1) of Example 1.
- FIG. FIG. 2 is an oxygen reduction current density-potential curve of the fuel cell electrode (1) of Example 1.
- FIG. 3 is a powder X-ray diffraction spectrum of the catalyst (2) of Example 2.
- 4 is an oxygen reduction current density-potential curve of the fuel cell electrode (2) of Example 2.
- FIG. 5 is a powder X-ray diffraction spectrum of the catalyst (3) of Example 3.
- 6 is an oxygen reduction current density-potential curve of the fuel cell electrode (3) of Example 3.
- FIG. FIG. 7 is a powder X-ray diffraction spectrum of the catalyst (4) of Example 4.
- FIG. 8 is an oxygen reduction current density-potential curve of the fuel cell electrode (4) of Example 4.
- FIG. 9 is a powder X-ray diffraction spectrum of the catalyst (5) of Example 5.
- FIG. 10 is an oxygen reduction current density-potential curve of the fuel cell electrode (5) of Example 5.
- FIG. 11 is a powder X-ray diffraction spectrum of the catalyst (6) of Example 6.
- FIG. 12 is an oxygen reduction current density-potential curve of the fuel cell electrode (6) of Example 6.
- FIG. 13 is a powder X-ray diffraction spectrum of the catalyst (7) of Example 7.
- FIG. 14 is an oxygen reduction current density-potential curve of the fuel cell electrode (7) of Example 7.
- FIG. 15 is the powder X-ray diffraction spectrum of the catalyst (8) of Example 8.
- FIG. 16 is an oxygen reduction current density-potential curve of the fuel cell electrode (8) of Example 8.
- FIG. 16 is an oxygen reduction current density-potential curve of the fuel cell electrode (8) of Example 8.
- FIG. 17 is the powder X-ray diffraction spectrum of the catalyst (9) of Example 9.
- FIG. 18 is an oxygen reduction current density-potential curve of the fuel cell electrode (9) of Example 9.
- FIG. 19 is the powder X-ray diffraction spectrum of the catalyst (10) of Example 10.
- FIG. 20 is an oxygen reduction current density-potential curve of the fuel cell electrode (10) of Example 10.
- FIG. 21 is the powder X-ray diffraction spectrum of the catalyst (11) of Example 11.
- FIG. 22 is an oxygen reduction current density-potential curve of the fuel cell electrode (11) of Example 11.
- FIG. 23 is the powder X-ray diffraction spectrum of the catalyst (12) of Example 12.
- FIG. 24 is an oxygen reduction current density-potential curve of the fuel cell electrode (12) of Example 12.
- FIG. 25 is the powder X-ray diffraction spectrum of the catalyst (13) of Example 13.
- FIG. 26 is an oxygen reduction current density-potential curve of the fuel cell electrode (13) of Example 13.
- FIG. 27 is the powder X-ray diffraction spectrum of the catalyst (14) of Example 14.
- FIG. 28 is an oxygen reduction current density-potential curve of the fuel cell electrode (14) of Example 14.
- FIG. 29 is the powder X-ray diffraction spectrum of the catalyst (15) of Example 15.
- FIG. 30 is an oxygen reduction current density-potential curve of the fuel cell electrode (15) of Example 15.
- FIG. 31 is the powder X-ray diffraction spectrum of the catalyst (16) of Example 16.
- FIG. 32 is an oxygen reduction current density-potential curve of the fuel cell electrode (16) of Example 16.
- FIG. 33 is a powder X-ray diffraction spectrum of the catalyst (17) of Example 17.
- FIG. 34 is an oxygen reduction current density-potential curve of a fuel cell electrode (17) of Example 17.
- FIG. 35 is the powder X-ray diffraction spectrum of the catalyst (18) of Example 18.
- FIG. 36 is an oxygen reduction current density-potential curve of a fuel cell electrode (18) in Example 18.
- FIG. 37 is the powder X-ray diffraction spectrum of the catalyst (19) of Example 19.
- FIG. 38 is an oxygen reduction current density-potential curve of a fuel cell electrode (19) of Example 19.
- FIG. 39 is the powder X-ray diffraction spectrum of the catalyst (20) of Example 20.
- 40 is an oxygen reduction current density-potential curve of a fuel cell electrode (20) of Example 20.
- FIG. 41 is the powder X-ray diffraction spectrum of the catalyst (21) of Example 21.
- 42 is an oxygen reduction current density-potential curve of the fuel cell electrode (21) of Example 21.
- FIG. 43 is the powder X-ray diffraction spectrum of the catalyst (22) of Example 22.
- FIG. 44 is an oxygen reduction current density-potential curve of a fuel cell electrode (22) of Example 22.
- FIG. 45 is the powder X-ray diffraction spectrum of the catalyst (23) of Example 23.
- 46 is an oxygen reduction current density-potential curve of a fuel cell electrode (23) in Example 23.
- FIG. FIG. 47 is the powder X-ray diffraction spectrum of the catalyst (24) of Example 24.
- 48 is an oxygen reduction current density-potential curve of a fuel cell electrode (24) of Example 24.
- FIG. FIG. 49 is a powder X-ray diffraction spectrum of the catalyst (25) of Example 25.
- 50 is an oxygen reduction current density-potential curve of a fuel cell electrode (25) in Example 25.
- FIG. FIG. 51 is the powder X-ray diffraction spectrum of the catalyst (26) of Example 26.
- 52 is an oxygen reduction current density-potential curve of a fuel cell electrode (26) of Example 26.
- FIG. 53 is the powder X-ray diffraction spectrum of the catalyst (27) of Example 27.
- 54 is an oxygen reduction current density-potential curve of a fuel cell electrode (27) of Example 27.
- FIG. FIG. 55 is the powder X-ray diffraction spectrum of the catalyst (28) of Example 28.
- FIG. 56 is an oxygen reduction current density-potential curve of a fuel cell electrode (28) of Example 28.
- FIG. FIG. 57 is the powder X-ray diffraction spectrum of the catalyst (29) of Example 29.
- 58 is an oxygen reduction current density-potential curve of a fuel cell electrode (29) of Example 29.
- FIG. FIG. 59 is a powder X-ray diffraction spectrum of the catalyst (30) of Example 30.
- FIG. 60 is an oxygen reduction current density-potential curve of the fuel cell electrode (30) of Example 30.
- 61 is the powder X-ray diffraction spectrum of the catalyst (31) of Example 31.
- FIG. 62 is an oxygen reduction current density-potential curve of a fuel cell electrode (31) of Example 31.
- FIG. 63 is a powder X-ray diffraction spectrum of the catalyst (32) of Example 32.
- 64 is an oxygen reduction current density-potential curve of a fuel cell electrode (32) of Example 32.
- FIG. 65 is the powder X-ray diffraction spectrum of the catalyst (33) of Example 33.
- 66 is an oxygen reduction current density-potential curve of a fuel cell electrode (33) of Example 33.
- FIG. 67 is an X-ray powder diffraction spectrum of the catalyst (34) of Example 34.
- FIG. 68 is an oxygen reduction current density-potential curve of a fuel cell electrode (34) of Example 34.
- FIG. FIG. 69 is a powder X-ray diffraction spectrum of the catalyst (35) of Example 35.
- FIG. 70 is an oxygen reduction current density-potential curve of a fuel cell electrode (35) of Example 35.
- FIG. FIG. 71 is the powder X-ray diffraction spectrum of the catalyst (36) of Example 36.
- 72 is an oxygen reduction current density-potential curve of a fuel cell electrode (36) of Example 36.
- FIG. FIG. 73 is the powder X-ray diffraction spectrum of the catalyst (37) of Example 37.
- 74 is an oxygen reduction current density-potential curve of a fuel cell electrode (37) of Example 37.
- FIG. FIG. 75 is the powder X-ray diffraction spectrum of the catalyst (38) of Example 38.
- 76 is an oxygen reduction current density-potential curve of a fuel cell electrode (38) of Example 38.
- FIG. 77 is a powder X-ray diffraction spectrum of the catalyst (39) of Example 39.
- 78 is an oxygen reduction current density-potential curve of a fuel cell electrode (39) of Example 39.
- FIG. FIG. 79 is a powder X-ray diffraction spectrum of the catalyst (40) of Example 40.
- 80 is an oxygen reduction current density-potential curve of a fuel cell electrode (40) of Example 40.
- FIG. FIG. 81 is the powder X-ray diffraction spectrum of the catalyst (41) of Example 41.
- 82 is an oxygen reduction current density-potential curve of a fuel cell electrode (41) of Example 41.
- FIG. FIG. 83 is a powder X-ray diffraction spectrum of the catalyst (42) of Example 42.
- FIG. 84 is an oxygen reduction current density-potential curve of a fuel cell electrode (42) of Example 42.
- FIG. 85 is the powder X-ray diffraction spectrum of the catalyst (43) of Example 43.
- FIG. 86 is an oxygen reduction current density-potential curve of a fuel cell electrode (43) of Example 43.
- FIG. FIG. 87 is the powder X-ray diffraction spectrum of the catalyst (44) of Example 44.
- 88 is an oxygen reduction current density-potential curve of a fuel cell electrode (44) of Example 44.
- FIG. FIG. 89 is the powder X-ray diffraction spectrum of the catalyst (45) of Example 45.
- 90 is an oxygen reduction current density-potential curve of a fuel cell electrode (45) of Example 45.
- FIG. FIG. FIG. 85 is the powder X-ray diffraction spectrum of the catalyst (43) of Example 43.
- FIG. 86 is an oxygen reduction current density-potential curve of a fuel cell electrode (43) of Example 43.
- FIG. 91 is the powder X-ray diffraction spectrum of the catalyst (46) of Example 46.
- 92 is an oxygen reduction current density-potential curve of a fuel cell electrode (46) of Example 46.
- FIG. 93 is an oxygen reduction current density-potential curve of the fuel cell electrode (c1) of Comparative Example 1.
- FIG. 94 is an oxygen reduction current density-potential curve of the fuel cell electrode (c2) of Comparative Example 2.
- FIG. 95 is an oxygen reduction current density-potential curve of the fuel cell electrode (c3) of Comparative Example 3.
- FIG. 96 is an oxygen reduction current density-potential curve of the fuel cell electrode (c4) of Comparative Example 4.
- 97 is an oxygen reduction current density-potential curve of the fuel cell electrode (c5) of Comparative Example 5.
- the method for producing the fuel cell electrode catalyst of the present invention comprises: A step (1) of obtaining a solution (also referred to as “catalyst precursor solution” in this specification) by mixing at least the metal compound (1), the nitrogen-containing organic compound (2), and a solvent; Step (2) for removing the solvent from the catalyst precursor solution, and Step (3) for obtaining an electrode catalyst by heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
- a solution also referred to as “catalyst precursor solution” in this specification
- Step (2) for removing the solvent from the catalyst precursor solution
- Step (3) for obtaining an electrode catalyst by heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
- the metal compound (1) is a metal compound (M1) containing a specific metal element M1
- M1 a metal compound (M1) containing a specific metal element M1
- at least one component other than the solvent has an oxygen atom (that is, when using the compound (3) described later, the compound (1), the compound (2) and the compound ( At least one of 3) has an oxygen atom, and when the compound (3) is not used, at least one of the compound (1) and the compound (2) has an oxygen atom).
- atoms and ions are described as “atoms” without strictly distinguishing them.
- step (1) at least a metal compound (1), a nitrogen-containing organic compound (2), a solvent, and optionally a compound (3) described later are mixed to obtain a catalyst precursor solution.
- the procedure (ii) is preferable.
- the metal compound (1) is, for example, a metal halide to be described later, the procedure (i) is preferable, and when the metal compound (1) is, for example, a metal alkoxide or a metal complex to be described later. Procedure (ii) is preferred.
- the mixing operation is preferably performed with stirring in order to increase the dissolution rate of each component in the solvent.
- the solution of the metal compound (1) is added little by little to the solution of the nitrogen-containing organic compound (2) or the solution of the nitrogen-containing organic compound (2) and the compound (3) (that is, the entire amount is once added). It is also preferable to not add to. If the transition metal compound (M12) described later is used, a solution of the nitrogen-containing organic compound (2) and the transition metal compound (M12), or the nitrogen-containing organic compound (2), the compound (3), and the transition metal It is also preferable to add the solution of the metal compound (M1) (excluding the transition metal compound (M12)) little by little (that is, do not add the whole amount at once) to the solution of the compound (M12).
- the catalyst precursor solution contains a reaction product of the metal compound (1) and the nitrogen-containing organic compound (2).
- the solubility of the reaction product in the solvent varies depending on the combination of the metal compound (1), the nitrogen-containing organic compound (2), the solvent, and the like.
- the catalyst precursor solution depends on the type of the solvent and the type of the nitrogen-containing organic compound (2). Even if it contains no dispersoids, these are small amounts (for example, 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less of the total amount of the solution).
- the catalyst precursor solution contains the metal compound (1), depending on the type of solvent and the type of the nitrogen-containing organic compound (2). Precipitates that are considered to be reaction products with the nitrogen-containing organic compound (2) tend to occur.
- step (1) the metal compound (1), the nitrogen-containing organic compound (2), a solvent, and optionally the compound (3) are placed in a pressurizable container such as an autoclave, and a pressure higher than normal pressure is applied. However, mixing may be performed.
- the temperature at which the metal compound (1), the nitrogen-containing organic compound (2), and a solvent are optionally mixed with the compound (3) is, for example, 0 to 60 ° C. It is estimated that a complex is formed from the metal compound (1) and the nitrogen-containing organic compound (2). If this temperature is excessively high, the complex is hydrolyzed when the solvent contains water, and the hydroxide It is considered that an excellent catalyst cannot be obtained. If the temperature is too low, the metal compound (1) is precipitated before the complex is formed, and an excellent catalyst cannot be obtained. it is conceivable that.
- the metal compound (1) is a metal compound (M1) containing the following metal element M1.
- the metal element M1 is a metal element selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten, and cerium.
- the metal elements M1 aluminum, chromium, iron, cobalt, copper, yttrium, tin and cerium are preferable, and copper is particularly preferable. These may be used alone or in combination of two or more.
- the metal compound (1) preferably has at least one selected from an oxygen atom and a halogen atom, and specific examples thereof include a metal phosphate, a metal sulfate, a metal nitrate, and a metal organic acid salt. , Metal acid halides (intermediate hydrolysates of metal halides), metal alkoxides, metal halides, metal halides and metal hypohalites, and metal complexes. These may be used alone or in combination of two or more.
- the metal alkoxide is preferably the metal methoxide, propoxide, isopropoxide, ethoxide, butoxide, or isobutoxide, and more preferably the metal isopropoxide, ethoxide, or butoxide.
- the metal alkoxide may have one type of alkoxy group or may have two or more types of alkoxy groups.
- metal compound (1) having an oxygen atom metal alkoxide, acetylacetone complex, metal acid chloride, metal sulfate and metal nitrate are preferable, and metal alkoxide and acetylacetone complex are more preferable from the viewpoint of cost. From the viewpoint of solubility, metal alkoxides and acetylacetone complexes are more preferable.
- metal halide metal chloride, metal bromide and metal iodide are preferable, and as the metal acid halide, metal acid chloride, metal acid bromide and metal acid iodide are preferable.
- the metal perhalogenate is preferably a metal perchlorate
- the metal hypohalite is preferably a metal hypochlorite
- the metal compound (M1) include Chromium (III) methoxide, Chromium (III) ethoxide, Chromium (III) propoxide, Chromium (III) isopropoxide, Chromium (III) butoxide, Chromium (III) isobutoxide, Chromium (III) pentoxide, Chromium (III) Acetylacetonate, chromium (III) isopropoxide acetylacetonate (Cr (acac) (O-iPr) 2 , Cr (acac) 2 (O-iPr), acac is acetylacetonate ion, iPr is isopropyl group The same shall apply hereinafter.), Trisdiethylaminochromium, tris (2,2,6,6-tetramethyl-3,5-heptanedione) chromium, chromium (III) hexafluoroacetylacetonate, tri-1
- the resulting catalyst becomes fine particles with a uniform particle size, and its activity is high, Chromium trichloride, chromium dichloride, chromium oxychloride, chromium (III) ethoxide, chromium (III) isopropoxide, chromium (III) butoxide, chromium (III) acetylacetonate, chromium (III) isopropoxide acetylacetonate (Cr (acac) (O-iPr) 2 , Manganese trichloride, manganese dichloride, manganese oxychloride, manganese (III) ethoxide, manganese (III) isopropoxide, manganese (III) butoxide, manganese (III) acetylacetonate, manganese (III) isopropoxide acetylacetonate (Mn (acac) (O-iPr) 2 , M
- the metal element M1 is not the metal element having the highest mole fraction of metal atoms (hereinafter also referred to as “metal element M11”).
- metal element M11 a transition metal compound (M12) containing a transition metal element M12 which is an element different from the metal element M11 and is at least one selected from iron, nickel, chromium, cobalt and manganese may be used.
- the transition metal compound (M12) is used, the performance of the resulting catalyst is improved.
- transition metal element M12 iron and chromium are preferable and iron is more preferable from the viewpoint of balance between cost and performance of the obtained catalyst.
- transition metal compound (M12) Iron (III) ethoxide, iron (III) isopropoxide acetylacetonate (Fe (acac) (O-iPr) 2 , Fe (acac) 2 (O-iPr)), iron (III) acetylacetonate, tris ( 2,2,6,6-tetramethyl-3,5-heptanedione) iron (III), iron (III) hexafluoroacetylacetonate, iron (II) chloride, iron (III) chloride, iron (III) sulfate , Iron sulfide (II), iron sulfide (III), potassium ferrocyanide, potassium ferricyanide, ammonium ferrocyanide, ammonium ferricyanide, iron ferrocyanide, iron nitrate (II), iron nitrate (III), iron oxalate ( II), iron (III) oxalate, iron (II)
- the range of ⁇ is preferably 0.01 ⁇ ⁇ . ⁇ 0.45, more preferably 0.02 ⁇ ⁇ ⁇ 0.4, and particularly preferably 0.05 ⁇ ⁇ ⁇ 0.3.
- a transition metal compound (M2) containing at least one transition metal element M2 selected from Group 4 and Group 5 elements of the periodic table as a metal element may be used in combination.
- transition metal element M2 examples include titanium, zirconium, hafnium, niobium, vanadium and tantalum, and titanium, zirconium, niobium, vanadium and tantalum are preferable from the viewpoint of cost and the performance of the obtained catalyst. And zirconium are more preferred. These may be used alone or in combination of two or more.
- transition metal compound (M2) examples include Titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetraisobutoxide, titanium tetrapentoxide, titanium tetraacetylacetonate, titanium diisopropoxide diacetylacetonate ( Ti (acac) 2 (O-iPr) 2 ) Titanium oxydiacetylacetonate, tris (acetylacetonato) dititanium chloride ([Ti (acac) 3 ] 2 [TiCl 6 ]), titanium tetrachloride, trichloride Titanium compounds such as titanium, titanium oxychloride, titanium tetrabromide, titanium tribromide, titanium oxybromide, titanium tetraiodide, titanium triiodide, titanium oxyiodide,
- the resulting catalyst becomes fine particles with a uniform particle size, and its activity is high, Titanium tetraethoxide, titanium tetrachloride, titanium oxychloride, titanium tetraisopropoxide, titanium tetraacetylacetonate, titanium diisopropoxide diacetylacetonate (Ti (acac) 2 (O-iPr) 2 ), Niobium pentaethoxide, niobium pentachloride, niobium oxychloride, niobium pentaisopropoxide, niobium pentaacetylacetonate, niobium triacetylacetonate, niobium diisopropoxide triacetylacetonate (Nb (acac) 3 (O-iPr 2 ), Zirconium tetraethoxide, zirconium tetrachloride, zirconium oxy
- the nitrogen-containing organic compound (2) is preferably a compound that can be a ligand capable of coordinating to the metal atom in the metal compound (1) (preferably a compound that can form a mononuclear complex). More preferred are compounds that can be bidentate (preferably bidentate or tridentate) (can form chelates).
- the nitrogen-containing organic compound (2) may be used alone or in combination of two or more.
- the nitrogen-containing organic compound (2) is preferably an amino group, nitrile group, imide group, imine group, nitro group, amide group, azide group, aziridine group, azo group, isocyanate group, isothiocyanate group, oxime group, Functional groups such as diazo group and nitroso group, or pyrrole ring, porphyrin ring, pyrrolidine ring, imidazole ring, triazole ring, pyridine ring, piperidine ring, pyrimidine ring, pyrazine ring, purine ring, etc. (these functional groups and rings) Are also referred to as “nitrogen-containing molecular groups”).
- the nitrogen-containing organic compound (2) has a nitrogen-containing molecular group in the molecule, the nitrogen-containing organic compound (2) can be more strongly coordinated with the metal atom derived from the metal compound (1) through mixing in the step (1). it is conceivable that.
- an amino group, an imine group, an amide group, a pyrrole ring, a pyridine ring and a pyrazine ring are more preferable, an amino group, an imine group, a pyrrole ring and a pyrazine ring are more preferable, and an amino group and a pyrazine ring are preferable.
- an amino group, an imine group, a pyrrole ring and a pyrazine ring are more preferable, and an amino group and a pyrazine ring are preferable.
- nitrogen-containing organic compound (2) examples include melamine, ethylenediamine, triazole, acetonitrile, acrylonitrile, ethyleneimine, aniline, pyrrole and polyethyleneimine, and salts thereof.
- nitrogen-containing organic compound (2) excluding oxygen atoms
- nitrogen-containing organic compound (2) include melamine, ethylenediamine, triazole, acetonitrile, acrylonitrile, ethyleneimine, aniline, pyrrole and polyethyleneimine, and salts thereof.
- ethylenediamine and ethylenediamine dihydrochloride are preferable because the resulting catalyst has high activity.
- the nitrogen-containing organic compound (2) is preferably further a hydroxyl group, a carboxyl group, an aldehyde group, an acid halide group, a sulfo group, a phosphoric acid group, a ketone group, an ether group or an ester group (these are collectively referred to as “oxygen-containing molecule”). It is also called a group.)
- oxygen-containing molecule a group that the nitrogen-containing organic compound (2) can be coordinated more strongly with the metal atom derived from the metal compound (1) through mixing in the step (1). .
- oxygen-containing molecular groups carboxyl groups and aldehyde groups are particularly preferable because the activity of the resulting catalyst is particularly high.
- the nitrogen-containing organic compound (2) containing an oxygen atom in the molecule a compound having the nitrogen-containing molecular group and the oxygen-containing molecular group is preferable. Such a compound is considered to be able to coordinate particularly strongly to the metal atom derived from the metal compound (1) through the step (1).
- amino acids having an amino group and a carboxyl group, and derivatives thereof are preferable.
- amino acids examples include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tryptophan, tyrosine, valine, norvaline, glycylglycine, Triglycine and tetraglycine are preferred, and the activity of the resulting catalyst is high. Alanine, glycine, lysine, methionine, and tyrosine are more preferred, and the resulting catalyst exhibits extremely high activity, so that alanine, glycine, and lysine are particularly preferred. preferable.
- nitrogen-containing organic compound (2) containing an oxygen atom in the molecule examples include acyl pyrroles such as acetyl pyrrole, acyl imidazoles such as pyrrole carboxylic acid and acetyl imidazole, Imidazole, imidazolecarboxylic acid, pyrazole, acetanilide, pyrazinecarboxylic acid, piperidinecarboxylic acid, piperazinecarboxylic acid, morpholine, pyrimidinecarboxylic acid, nicotinic acid, 2-pyridinecarboxylic acid, 2,4-pyridinedicarboxylic acid, 8-quinolinol, and Polyvinylpyrrolidone and the like, and since the resulting catalyst has high activity, compounds that can be bidentate ligands, such as pyrrole-2-carboxylic acid, imidazole-4-carboxylic acid, 2-pyrazinecarboxylic acid, 2 -Pi
- the ratio of the total number of carbon atoms B in the nitrogen-containing organic compound (2) used in the step (1) to the total number of metal atoms A in the metal compound (1) used in the step (1) can reduce the amount of components desorbed as carbon compounds such as carbon dioxide and carbon monoxide during the heat treatment in step (3), that is, the amount of exhaust gas can be reduced during catalyst production.
- it is 200 or less, more preferably 150 or less, further preferably 80 or less, particularly preferably 30 or less, and preferably 1 or more, more preferably 2 or more, and still more preferably from the viewpoint of obtaining a catalyst with good activity.
- Ratio of the total number of atoms C of nitrogen of the nitrogen-containing organic compound (2) used in step (1) to the total number of atoms A of the metal elements of the metal compound (1) used in step (1) is preferably 28 or less, more preferably 17 or less, still more preferably 12 or less, particularly preferably 8.5 or less, from the viewpoint of obtaining a catalyst having a good activity, and a catalyst having a good activity is obtained. From the viewpoint, it is preferably 1 or more, more preferably 2.5 or more, still more preferably 3 or more, and particularly preferably 3.5 or more.
- an electrode catalyst having higher catalytic activity can be produced by further mixing the following compound (3) in step (1).
- the compound (3) containing at least one element A selected from the group consisting of boron, phosphorus and sulfur and fluorine (3) include boric acid derivatives containing fluorine, phosphoric acid derivatives containing fluorine, fluorine Examples thereof include sulfonic acid derivatives.
- Tetrafluoroboric acid quaternary ammonium salts eg, tetra-n-butylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrafluoroborate tetra Butyl ammonium, ethyl trimethyl ammonium tetrafluoroborate, diethyl dimethyl ammonium tetrafluoroborate, triethyl methyl ammonium tetrafluoroborate, methyl tripropyl ammonium tetrafluoroborate, ethyl tripropyl ammonium tetrafluoroborate, trimethyl tetrafluoroborate Propyl ammonium, ethyl dimethylpropyl ammonium tetrafluoroborate, te
- boric acid derivative containing fluorine preferably, ammonium tetrafluoroborate, methylammonium tetrafluoroborate, dimethylammonium tetrafluoroborate, trimethylammonium tetrafluoroborate, ethylammonium tetrafluoroborate, tetrafluoroborate Diethylammonium acid, triethylammonium tetrafluoroborate, butylammonium tetrafluoroborate, dibutylammonium tetrafluoroborate, tributylammonium tetrafluoroborate, tetra-n-butylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate Tetrafluoroammonium tetrafluoroborate, Tetrapropylammonium tetrafluoroborate, Tetrafluoro Preferred are tetrabutyl
- Hexafluorophosphates such as hexafluorophosphate quaternary ammonium salts (eg tetra-n-butylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrahexafluorophosphate)
- hexafluorophosphate quaternary ammonium salts eg tetra-n-butylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrahexafluorophosphate
- Propylammonium tetrabutylammonium hexafluorophosphate, ethyltrimethylammonium hexafluorophosphate, dieth
- Fluoroalkyl phosphoric acid amide A fluoroalkylphosphorous acid represented by the general formula (RO) 3 P, (RO) 2 (OH) P, or (RO) (OH) 2 P (wherein the above-mentioned fluoroalkyl group is represented), A fluoroalkyl phosphite amide represented by the general formula (RN) 3 P, (RN) 2 P (OH), (RN) P (OH) 2 (wherein R represents the fluoroalkyl group), A fluoroalkylphosphonic acid represented by the general formula: RPO (OH) 2 (wherein R represents the fluoroalkyl group). Is mentioned.
- the phosphoric acid derivative containing fluorine is preferably ammonium hexafluorophosphate, methylammonium hexafluorophosphate, dimethylammonium hexafluorophosphate, trimethylammonium hexafluorophosphate, ethylammonium hexafluorophosphate, hexafluorophosphoric acid Diethylammonium, triethylammonium hexafluorophosphate, butylammonium hexafluorophosphate, dibutylammonium hexafluorophosphate, tributylammonium hexafluorophosphate, tetra-n-butylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, Tetrafluoroammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphat
- a copolymer of tetrafluoroethylene and perfluoro [2- (fluorosulfonylethoxy) propyl vinyl ether] for example, NAFION (registered trademark), a copolymer having a structure represented by the following formula)
- Fluoroalkylsulfonic acid in which all or part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (for example, nonacosadecafluorotetradecanesulfonic acid, heptacosadecafluoro Tridecanesulfonic acid, pentacosadecafluorododecanesulfonic acid, tricosadecafluoroundecanesulfonic acid, henicosadecafluorodecanesulfonic acid, nonadecafluorononanesulfonic acid, heptadecafluorooctanesulfonic acid, pentadecafluoroheptanesulfonic acid , Tridecafluorohexanesulfonic acid, undecafluoropentanesulfonic acid, nonafluorobutanesulfonic acid, hept
- the fluorine-containing sulfonic acid derivative is preferably a copolymer of tetrafluoroethylene and perfluoro [2- (fluorosulfonylethoxy) propyl vinyl ether] (for example, NAFION (registered trademark)), heptadeca Fluorooctanesulfonic acid, pentadecafluoroheptanesulfonic acid, tridecafluorohexanesulfonic acid, undecafluoropentanesulfonic acid, nonafluorobutanesulfonic acid, heptafluoropropanesulfonic acid, pentafluoroethanesulfonic acid, trifluoromethanesulfonic acid, hepta Ammonium decafluorooctane sulfonate, ammonium pentadecafluoroheptane sulfonate, ammonium tridecafluorohexane sulfon
- the amount of the element A contained in the compound (3) used in the step (1) (that is, the element A contained in the compound (3) used in the step (1).
- the total number of atoms) is usually 0.01 to 3 mol, preferably 0.01 to 2 mol, more preferably, relative to 1 mol of the metal atom in the metal compound (1) used in step (1). 0.01 to 1 mol.
- the amount is usually 0.01 to 3 mol, preferably 0.01 to 2 mol, more preferably 0.01 to 1 mol, based on the above criteria, and element A is phosphorus.
- the amount is usually 0.01 to 3 mol, preferably 0.01 to 2 mol, more preferably 0.01 to 1 mol, based on the above criteria, and when element A is only sulfur.
- the amount is usually 0.01 to 3 mol, preferably 0.01 to 2 mol, more preferably 0.01 to 1 mol, based on the above criteria.
- the amount of fluorine contained in the compound (3) used in the step (1) (that is, the total number of fluorine atoms contained in the compound (3) used in the step (1)) is used in the step (1).
- the amount is usually 0.01 to 5 mol, preferably 0.02 to 4 mol, more preferably 0.03 to 3 mol, relative to 1 mol of the metal atom in the metal compound (1).
- the amount of the compound (3) is an amount when the raw materials other than the compound (3) used in the step (1) do not contain the element A or fluorine, and the raw materials other than the compound (3) are the element A or In the case of containing fluorine, it is preferable to appropriately reduce the amount of the compound (3) used in the step (1).
- solvent examples include water, alcohols and acids.
- alcohols examples include ethanol, methanol, butanol, propanol and ethoxyethanol are preferable, and ethanol and methanol are more preferable.
- acids acetic acid, nitric acid (aqueous solution), hydrochloric acid, phosphoric acid aqueous solution and citric acid aqueous solution are preferable, and acetic acid and nitric acid are more preferable. These may be used alone or in combination of two or more.
- Methanol is preferred as the solvent when the metal compound (1) is a metal halide.
- the solvent may be used in an amount such as 50 to 95% by weight in 100% by weight of the catalyst precursor solution.
- ⁇ Precipitation inhibitor> When the metal compound (1) contains a halogen atom, these compounds are generally easily hydrolyzed by water, and precipitates such as hydroxides and acid chlorides are easily generated. Therefore, when the metal compound (1) contains a halogen atom, it is preferable to add a strong acid in the solution (catalyst precursor solution) in an amount of 1% by weight or more.
- a strong acid in the solution for example, when the acid is hydrochloric acid, the acid is added to the metal compound (1) by adding an acid such that the concentration of hydrogen chloride in the solution (catalyst precursor solution) is 5 wt% or more, more preferably 10 wt% or more.
- a clear catalyst precursor solution can be obtained while suppressing the occurrence of precipitation of the derived hydroxide, acid chloride and the like.
- a catalyst precursor solution may be obtained without using an alcohol alone as the solvent and without adding an acid.
- the metal compound (1) is a metal complex and water is used alone or water and another compound as the solvent, it is possible to suppress the occurrence of precipitation of hydroxide or acid chloride. It is preferable to use a precipitation inhibitor.
- the precipitation inhibitor is preferably a compound having a diketone structure, more preferably diacetyl, acetylacetone, 2,5-hexanedione and dimedone, and further preferably acetylacetone and 2,5-hexanedione.
- These precipitation inhibitors are preferably 1 to 70% by weight in 100% by weight of a metal compound solution (a solution containing the metal compound (1) and not containing the nitrogen-containing organic compound (2) and the compound (3)). %, More preferably 2 to 50% by weight, still more preferably 15 to 40% by weight.
- precipitation inhibitors are preferably used in an amount of 0.1 to 40% by weight, more preferably 0.5 to 20% by weight, and further preferably 2 to 10% by weight in 100% by weight of the catalyst precursor solution. Added.
- the precipitation inhibitor may be added at any stage in step (1).
- step (1) preferably, a solution containing the metal compound (1) and the precipitation inhibitor is prepared, and then the solution, the nitrogen-containing organic compound (2) and optionally the compound (3) are combined. Mix to obtain a catalyst precursor solution.
- the step (1) is performed, the occurrence of the precipitation can be suppressed more reliably.
- step (2) the solvent is removed from the catalyst precursor solution obtained in step (1).
- the removal of the solvent may be performed in the atmosphere or in an inert gas (for example, nitrogen, argon, helium) atmosphere.
- an inert gas for example, nitrogen, argon, helium
- nitrogen and argon are preferable from the viewpoint of cost, and nitrogen is more preferable.
- the temperature at the time of solvent removal may be room temperature when the vapor pressure of the solvent is high, but from the viewpoint of mass production of the catalyst, it is preferably 30 ° C or higher, more preferably 40 ° C or higher, and still more preferably.
- the catalyst precursor which is estimated to be a metal complex such as a chelate, contained in the solution obtained in step (1) at 50 ° C or higher, preferably 350 ° C or lower, more preferably It is 150 degrees C or less, More preferably, it is 110 degrees C or less.
- the removal of the solvent may be performed under atmospheric pressure when the vapor pressure of the solvent is high, but in order to remove the solvent in a shorter time, it is performed under reduced pressure (for example, 0.1 Pa to 0.1 MPa). Also good.
- reduced pressure for example, 0.1 Pa to 0.1 MPa.
- an evaporator can be used to remove the solvent under reduced pressure.
- the solvent may be removed while the mixture obtained in the step (1) is left standing, but in order to obtain a more uniform solid residue, it is preferable to remove the solvent while rotating the mixture. .
- the composition or aggregation state of the solid residue obtained in the step (2) may be different. May be non-uniform. In such a case, a catalyst having a more uniform particle size can be obtained by mixing and crushing the solid residue and using a more uniform and fine powder in step (3).
- solid residue for example, roll rolling mill, ball mill, small diameter ball mill (bead mill), medium stirring mill, airflow crusher, mortar, automatic kneading mortar, tank crusher, jet mill If the solid residue is small, preferably, a mortar, an automatic kneading mortar, or a batch type ball mill is used, and when the solid residue is large and continuous mixing and crushing are performed.
- a jet mill is preferably used.
- step (3) the solid residue obtained in the step (2) is heat-treated to obtain an electrode catalyst.
- the temperature during this heat treatment is 500 to 1100 ° C., preferably 600 to 1050 ° C., more preferably 700 to 950 ° C.
- the temperature of the heat treatment is too higher than the above range, sintering and grain growth occur between the particles of the obtained electrode catalyst, resulting in a decrease in the specific surface area of the electrode catalyst. As a result, the processability during processing into a catalyst layer is poor. On the other hand, if the temperature of the heat treatment is too lower than the above range, an electrode catalyst having high activity cannot be obtained.
- Examples of the heat treatment method include a stationary method, a stirring method, a dropping method, and a powder trapping method.
- the standing method is a method in which the solid residue obtained in the step (2) is placed in a stationary electric furnace or the like and heated.
- the solid content residue weighed during heating may be put in a ceramic container such as an alumina board or a quartz board.
- the stationary method is preferable in that a large amount of the solid residue can be heated.
- the stirring method is a method in which the solid residue is placed in an electric furnace such as a rotary kiln and heated while stirring.
- the stirring method is preferable in that a large amount of the solid residue can be heated and aggregation and growth of the obtained electrode catalyst particles can be suppressed.
- the stirring method is preferable in that the electrode catalyst can be continuously produced by inclining the heating furnace.
- the dropping method an atmospheric gas is passed through an induction furnace, the furnace is heated to a predetermined heating temperature, and after maintaining a thermal equilibrium at the temperature, the solid residue is placed in a crucible that is a heating area of the furnace. It is a method of dropping and heating this.
- the dropping method is preferred in that aggregation and growth of the obtained electrocatalyst particles can be minimized.
- Powder capture method is an inert gas atmosphere containing a small amount of oxygen gas, the solid residue is splashed and suspended, captured in a vertical tube furnace maintained at a predetermined heating temperature, It is a method of heating.
- the rate of temperature rise is not particularly limited, but is preferably about 1 ° C./min to 100 ° C./min, more preferably 5 ° C./min to 50 ° C./min. is there.
- the heating time is preferably 0.1 to 10 hours, more preferably 0.5 hours to 5 hours, and further preferably 0.5 to 3 hours.
- the heating time for the solid residue is 0.1 to 10 hours, preferably 0.5 to 5 hours.
- uniform electrode catalyst particles tend to be formed.
- the heating time of the solid residue is usually 10 minutes to 5 hours, preferably 30 minutes to 2 hours.
- the average residence time calculated from the steady sample flow rate in the furnace is set as the heating time.
- the heating time of the solid residue is usually 0.5 to 10 minutes, preferably 0.5 to 3 minutes.
- the heating time is within the above range, uniform electrode catalyst particles tend to be formed.
- the heating time of the solid residue is 0.2 seconds to 1 minute, preferably 0.2 to 10 seconds.
- the heating time is within the above range, uniform electrode catalyst particles tend to be formed.
- a heating furnace using LNG (liquefied natural gas), LPG (liquefied petroleum gas), light oil, heavy oil, electricity or the like as a heat source may be used as the heat treatment apparatus.
- LNG liquefied natural gas
- LPG liquefied petroleum gas
- light oil a heating furnace using LNG (liquefied natural gas), LPG (liquefied petroleum gas), light oil, heavy oil, electricity or the like as a heat source
- the fuel flame is present in the furnace, and is not heated from the inside of the furnace, but is heated from the outside of the furnace.
- An apparatus is preferred.
- a heating furnace using LNG or LPG as a heat source is preferable from the viewpoint of cost.
- Examples of the shape of the furnace include a tubular furnace, an upper lid furnace, a tunnel furnace, a box furnace, a sample table raising / lowering furnace (elevator type), a cart furnace, and the like, and the atmosphere can be controlled particularly strictly.
- Tubular furnaces, top lid furnaces, box furnaces and sample table raising / lowering furnaces are preferred, and tubular furnaces and box furnaces are preferred.
- the above heat source can be used, but the scale of the equipment is large when the solid residue is continuously heat-treated by inclining the rotary kiln among the stirring methods. Therefore, it is preferable to use a heat source derived from a fuel such as LPG because the amount of energy used tends to increase.
- the atmosphere for the heat treatment is preferably an atmosphere whose main component is an inert gas from the viewpoint of increasing the activity of the obtained electrode catalyst.
- an inert gas nitrogen, argon, and helium are preferable and nitrogen and argon are more preferable because they are relatively inexpensive and easily available.
- These inert gas may be used individually by 1 type, and may mix and use 2 or more types.
- These gases are generally called inert gases, but these inert gases, that is, nitrogen, argon, helium, and the like during the heat treatment in the step (3) are separated from the solid residue. It may be reacting.
- the obtained electrode catalyst may exhibit higher catalytic performance.
- the heat treatment is performed using nitrogen gas, argon gas, a mixed gas of nitrogen gas and argon gas, or one or more gases selected from nitrogen gas and argon gas, and one or more selected from hydrogen gas, ammonia gas, and oxygen gas.
- nitrogen gas argon gas
- a mixed gas of nitrogen gas and argon gas or one or more gases selected from nitrogen gas and argon gas, and one or more selected from hydrogen gas, ammonia gas, and oxygen gas.
- the hydrogen gas concentration is, for example, 100% by volume or less, preferably 0.01 to 10% by volume, more preferably 1 to 5% by volume.
- the concentration of oxygen gas is, for example, 0.01 to 10% by volume, preferably 0.01 to 5% by volume.
- the pressure during the heat treatment is not particularly limited, and the heat treatment may be performed under atmospheric pressure in consideration of manufacturing stability and cost.
- the heat treatment product may be crushed.
- pulverization it may be possible to improve the workability in producing an electrode using the obtained electrode catalyst and the characteristics of the obtained electrode.
- a roll rolling mill for example, a ball mill, a small-diameter ball mill (bead mill), a medium stirring mill, an airflow grinder, a mortar, an automatic kneading mortar, a tank disintegrator, or a jet mill can be used.
- a mortar, an automatic kneading mortar, or a batch type ball mill is preferable.
- a heat-treated product is continuously processed in a large amount, a jet mill or a continuous type ball mill is preferable, and a continuous type ball mill is used. Among these, a bead mill is more preferable.
- the heat-treated product of the present invention is At least a metal compound (1), a nitrogen-containing organic compound (2), a solvent, and optionally a compound (3) containing at least one element A selected from the group consisting of boron, phosphorus and sulfur and fluorine.
- a metal compound (1) a nitrogen-containing organic compound (2)
- a solvent a solvent
- a compound (3) containing at least one element A selected from the group consisting of boron, phosphorus and sulfur and fluorine is obtained at a temperature of 500 to 1100 ° C.
- the metal compound (1) Obtained through A part or all of the metal compound (1) is a metal compound (M1) containing at least one metal element M1 selected from Group 4 and Group 5 elements of the periodic table as a metal element, Of the components used in the step (1), at least one component other than the solvent has an oxygen atom (that is, when the compound (3) is used, the compound (1), the compound (2) and the compound (3 ) Has an oxygen atom, and when compound (3) is not used, at least one of compound (1) and compound (2) has an oxygen atom) It is characterized by that.
- M1 metal compound containing at least one metal element M1 selected from Group 4 and Group 5 elements of the periodic table as a metal element
- the heat-treated product of the present invention is useful as a fuel cell electrode catalyst to be described later.
- the fuel cell electrode catalyst of the present invention (hereinafter also simply referred to as “catalyst”) is characterized by being produced by the above-described method for producing a fuel cell electrode catalyst of the present invention. Moreover, the catalyst of this invention may consist of the heat-processing thing of this invention mentioned above.
- the range of x is more preferably 0.15 ⁇ x ⁇ 9.0, still more preferably 0.2 ⁇ x ⁇ 8.0, particularly preferably 1.0 ⁇ x ⁇ 7.0
- the range of y is more preferably 0.01 ⁇ y ⁇ 2.0, further preferably 0.02 ⁇ y ⁇ 1.8, particularly preferably 0.03 ⁇ y ⁇ 1.5
- the range of z is more preferably 0.05 ⁇ z ⁇ 5.0, further preferably 0.1 ⁇ z ⁇ 4.0, and particularly preferably 0.2 ⁇ z ⁇ 3.5.
- the range of a is more preferably 0.001 ⁇ a ⁇ 1, more preferably 0.001 ⁇ a ⁇ 0.5, and particularly preferably 0.001 ⁇ a ⁇ 0.2.
- the range of b is more preferably 0.0001 ⁇ b ⁇ 2, more preferably 0.001 ⁇ b ⁇ 1, and particularly preferably 0.001 ⁇ b ⁇ 0.2.
- the metal element is not the metal element M11 (the metal element having the highest metal atom mole fraction among the metal elements M1)
- the transition metal element M12 when included, when the ratio of the number of atoms of the transition metal element M12 to the number of atoms of the metal element M1 constituting the catalyst is represented by ⁇ , preferably 0 ⁇ ⁇ 0.45. In view of the high activity of the electrode catalyst, 0.01 ⁇ ⁇ ⁇ 0.45, more preferably 0.02 ⁇ ⁇ ⁇ 0.4, and particularly preferably 0.05 ⁇ ⁇ ⁇ 0.3. .
- the catalyst may contain atoms of the transition metal element M2, and the ratio of the number of atoms of the metal element M1 and the transition metal element M2 constituting the catalyst is expressed by the metal element M1: transition metal.
- ⁇ , x, y, z, a and b are values measured by the method employed in the examples described later.
- a fuel cell electrode catalyst having a large specific surface area is produced, and the specific surface area calculated by the BET method of the catalyst of the present invention is preferably 30 to 1000 m 2 / g, more preferably 30 to 350 m 2 / g, still more preferably 50 to 300 m 2 / g, and particularly preferably 100 to 300 m 2 / g.
- the oxygen reduction initiation potential of the catalyst (A) measured according to the following measurement method (A) is preferably 0.6 V (vs. RHE) or more, more preferably 0.7 V (vs. RHE) or more, more preferably 0.8 V (vs. RHE) or more, particularly preferably 0.85 V (vs. RHE) or more.
- carbon carbon black (specific surface area: 100 to 300 m 2 / g) (for example, VULCAN (registered trademark) XC72 manufactured by Cabot Corporation) is used, and the catalyst and carbon are dispersed so that the mass ratio is 95: 5.
- a reversible hydrogen electrode in a sulfuric acid aqueous solution of the same concentration at a temperature of 30 ° C. in a 0.5 mol / L sulfuric acid aqueous solution in an oxygen atmosphere and a nitrogen atmosphere was used as a reference electrode.
- a current-potential curve is measured by polarization at a potential scanning speed of 5 mV / sec, a difference of 0.2 ⁇ A / cm 2 or more appears between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere.
- the starting potential is defined as the oxygen reduction starting potential.
- the oxygen reduction current density can be determined as follows.
- a difference between a reduction current in an oxygen atmosphere and a reduction current in a nitrogen atmosphere at a specific potential is calculated from the result of the measurement method (A).
- a value obtained by dividing the calculated value by the electrode area is defined as an oxygen reduction current density (mA / cm 2 ).
- the catalyst of the present invention can be used as an alternative catalyst for a platinum catalyst.
- the fuel cell catalyst layer of the present invention is characterized by containing the catalyst.
- the fuel cell catalyst layer includes an anode catalyst layer and a cathode catalyst layer, and the catalyst can be used for both. Since the catalyst is excellent in durability and has a large oxygen reducing ability, it is preferably used in the cathode catalyst layer.
- the fuel cell catalyst layer of the present invention preferably further contains an electron conductive powder.
- the reduction current can be further increased.
- the electron conductive powder is considered to increase the reduction current because it causes an electrical contact for inducing an electrochemical reaction in the catalyst.
- the electron conductive particles are usually used as a catalyst carrier.
- the catalyst has a certain degree of conductivity, but in order to give more electrons to the catalyst, or in order for the reaction substrate to receive more electrons from the catalyst, the catalyst is mixed with carrier particles for imparting conductivity. Also good. These carrier particles may be mixed with the catalyst produced through the steps (1) to (3), or may be mixed at any stage of the steps (1) to (3).
- the material of the electron conductive particles examples include carbon, a conductive polymer, a conductive ceramic, a metal, or a conductive inorganic oxide such as tungsten oxide or iridium oxide, which can be used alone or in combination. .
- the electron conductive particles made of carbon have a large specific surface area, and are easily available with a small particle size at low cost, and are excellent in chemical resistance and high potential resistance, carbon alone or carbon and other electrons.
- a mixture with conductive particles is preferred. That is, the fuel cell catalyst layer preferably contains the catalyst and carbon.
- Examples of carbon include carbon black, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, porous carbon, and graphene. If the particle size of the electron conductive particles made of carbon is too small, it becomes difficult to form an electron conduction path. If the particle size is too large, the gas diffusibility of the fuel cell catalyst layer and the catalyst utilization rate tend to decrease. Therefore, the thickness is preferably 10 to 1000 nm, more preferably 10 to 100 nm.
- the weight ratio of the catalyst to the electron conductive particles is preferably 4: 1 to 1000: 1.
- the conductive polymer is not particularly limited.
- polypyrrole, polyaniline, and polythiophene are preferable, and polypyrrole is more preferable.
- the fuel cell catalyst layer of the present invention preferably further contains a polymer electrolyte.
- the polymer electrolyte is not particularly limited as long as it is generally used in a fuel cell catalyst layer.
- a perfluorocarbon polymer having a sulfonic acid group for example, NAFION (registered trademark)
- a hydrocarbon-based polymer compound having a sulfonic acid group for example, NAFION (registered trademark)
- a highly doped inorganic acid such as phosphoric acid.
- examples thereof include molecular compounds, organic / inorganic hybrid polymers partially substituted with proton conductive functional groups, and proton conductors in which a polymer matrix is impregnated with a phosphoric acid solution or a sulfuric acid solution.
- Nafion registered trademark
- NAFION registered trademark
- 5% Nafion (NAFION (registered trademark)) solution DE521, DuPont
- the fuel cell catalyst layer of the present invention can be used for either an anode catalyst layer or a cathode catalyst layer.
- the catalyst layer for a fuel cell of the present invention includes a catalyst layer (catalyst catalyst for cathode) provided on the cathode of a fuel cell because it contains a catalyst having high oxygen reducing ability and hardly corroded even in a high potential in an acidic electrolyte. Layer).
- a catalyst layer provided on the cathode of a membrane electrode assembly provided in a polymer electrolyte fuel cell.
- Examples of the method for dispersing the catalyst on the electron conductive particles as a support include air flow dispersion and dispersion in liquid. Dispersion in liquid is preferable because a catalyst and electron conductive particles dispersed in a solvent can be used in the fuel cell catalyst layer forming step. Examples of the dispersion in the liquid include a method using an orifice contraction flow, a method using a rotating shear flow, and a method using an ultrasonic wave.
- the solvent used for dispersion in the liquid is not particularly limited as long as it does not erode the catalyst or electron conductive particles and can be dispersed, but a volatile liquid organic solvent or water is generally used.
- the electrolyte and the dispersant may be further dispersed at the same time.
- the method for forming the catalyst layer for the fuel cell is not particularly limited. For example, a method of applying a suspension containing the catalyst, the electron conductive particles, and the electrolyte to the electrolyte membrane or the gas diffusion layer to be described later. It is done. Examples of the application method include a dipping method, a screen printing method, a roll coating method, and a spray method. In addition, after forming a catalyst layer for a fuel cell on a base material by a coating method or a filtration method using a suspension containing the catalyst, electron conductive particles, and an electrolyte, the catalyst layer for a fuel cell is formed on the electrolyte membrane by a transfer method. The method of forming is mentioned.
- the electrode of the present invention is characterized by having the fuel cell catalyst layer and a porous support layer.
- the electrode of the present invention can be used as either a cathode or an anode. Since the electrode of the present invention is excellent in durability and has a large catalytic ability, it is more industrially superior when used as a cathode.
- the porous support layer is a layer that diffuses gas (hereinafter also referred to as “gas diffusion layer”).
- gas diffusion layer may be anything as long as it has electron conductivity, high gas diffusibility, and high corrosion resistance.
- carbon-based porous materials such as carbon paper and carbon cloth are used. Materials and aluminum foil coated with stainless steel and corrosion-resistant materials for weight reduction are used.
- the membrane electrode assembly of the present invention is a membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is the electrode. It is characterized by that.
- the catalytic ability of the membrane electrode assembly can be evaluated by, for example, the maximum power density calculated as follows.
- the membrane electrode assembly 11 is fixed with bolts across a sealing material (gasket 12), a separator 13 with a gas flow path, and a current collector plate 14, and tightened to a predetermined surface pressure (4N).
- a sealing material gasket 12
- separator 13 with a gas flow path
- current collector plate 14 and tightened to a predetermined surface pressure (4N).
- a single cell of a polymer electrolyte fuel cell is created.
- Hydrogen was supplied to the anode side as a fuel at a flow rate of 1 liter / minute, oxygen was supplied to the cathode side as an oxidant at a flow rate of 2 liters / minute, and a back pressure of 300 kPa was applied on both sides while the single cell temperature was 90 ° C. Measure current-voltage characteristics.
- the maximum power density is calculated from the obtained current-voltage characteristic curve. The larger the maximum power density, the higher the catalytic ability of the membrane electrode assembly.
- the maximum power density is preferably 400 mW / cm 2 or more, more preferably 600 mW / cm 2 or more, the upper limit is, for example 1000 mW / cm 2 approximately.
- an electrolyte membrane using a perfluorosulfonic acid system or a hydrocarbon electrolyte membrane is generally used.
- a membrane or porous body in which a polymer microporous membrane is impregnated with a liquid electrolyte is used.
- a membrane filled with a polymer electrolyte may be used.
- the fuel cell of the present invention is characterized by comprising the membrane electrode assembly.
- Fuel cell electrode reactions occur at the so-called three-phase interface (electrolyte-electrode catalyst-reaction gas). Fuel cells are classified into several types depending on the electrolyte used, etc., and include molten carbonate type (MCFC), phosphoric acid type (PAFC), solid oxide type (SOFC), and solid polymer type (PEFC). . Especially, it is preferable to use the membrane electrode assembly of this invention for a polymer electrolyte fuel cell.
- MCFC molten carbonate type
- PAFC phosphoric acid type
- SOFC solid oxide type
- PEFC solid polymer type
- the fuel cell using the catalyst of the present invention has high performance and is extremely inexpensive compared to the case where platinum is used as a catalyst.
- the fuel cell of the present invention has at least one function selected from the group consisting of a power generation function, a light emission function, a heat generation function, a sound generation function, an exercise function, a display function, and a charge function,
- the performance of the portable article can be improved.
- the fuel cell is preferably provided on the surface or inside of an article.
- Specific example of article provided with fuel cell of the present invention include buildings, houses, buildings such as tents, fluorescent lamps, LEDs, etc., organic EL, street lamps, indoor lighting, lighting fixtures such as traffic lights, machines, Automotive equipment including the vehicle itself, home appliances, agricultural equipment, electronic equipment, portable information terminals including mobile phones, beauty equipment, portable tools, sanitary equipment such as bathroom accessories, furniture, toys, decorations, bulletin boards , Outdoor supplies such as cooler boxes, outdoor generators, teaching materials, artificial flowers, objects, power supplies for cardiac pacemakers, power supplies for heating and cooling devices with Peltier elements.
- the noise (N) is the width of the baseline.
- ⁇ Metal> About 0.1 g of the sample was weighed into a quartz beaker, and the sample was completely thermally decomposed using sulfuric acid, nitric acid and hydrofluoric acid. After cooling, the solution was made up to a volume of 100 ml, further diluted as appropriate, and quantified using ICP-OES (VISA-PRO by SII) or ICP-MS (HP7500 by Agilent).
- ICP-OES VISA-PRO by SII
- ICP-MS HP7500 by Agilent
- Combustion decomposition conditions Sample combustion apparatus: AQF-100 (Mitsubishi Chemical Analytech Co., Ltd.) Combustion tube temperature: 950 ° C (temperature decomposition by moving the sample board) Ion chromatography measurement conditions Measuring device: DIONEX DX-500 Eluent: 1.8 mM Na 2 CO 3 +1.7 mM NaHCO 3 Column (temperature): ShodexSI-90 (room temperature) Flow rate: 1.0 ml / min Injection volume: 25 ⁇ l Detector: Electrical conductivity detector Suppressor: DIONEX ASRS-300 ⁇ Boron> After adding phosphoric acid, several tens mg of the sample was heated until sulfuric acid was added and white smoke of sulfuric acid was generated, and the mixture was allowed to cool.
- BET specific surface area measurement BET specific surface area was measured using Micromeritics Gemini 2360 manufactured by Shimadzu Corporation. The pretreatment time and pretreatment temperature were set at 30 ° C. and 200 ° C., respectively.
- Example 1 Production of catalyst 2.60 g (25.94 mmol) of acetylacetone was placed in a beaker, and 6.25 g (17.59 mmol) of tin (IV) isopropoxide was added thereto while stirring, and 28 ml of acetic acid was further added dropwise over 2 minutes. A tin solution (1) was prepared.
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, and the solvent was slowly evaporated while heating and stirring the catalyst precursor solution.
- the solid residue obtained by completely evaporating the solvent was ground in an automatic mortar to obtain 13.0 g of powder for firing (1).
- the powder X-ray diffraction spectrum of the catalyst (1) is shown in FIG.
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (1) and the BET specific surface area of the catalyst (1).
- the produced fuel cell electrode (1) was polarized in an oxygen atmosphere and a nitrogen atmosphere in a 0.5 mol / L sulfuric acid aqueous solution at 30 ° C. and a potential scanning rate of 5 mV / sec. A potential curve was measured. At that time, a reversible hydrogen electrode in an aqueous sulfuric acid solution having the same concentration was used as a reference electrode.
- a potential at which a difference of 0.2 ⁇ A / cm 2 or more began to appear between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere was defined as the oxygen reduction start potential. Further, the difference between the reduction current in an oxygen atmosphere and the reduction current in a nitrogen atmosphere at 0.80 V (vs RHE) was calculated. A value obtained by further dividing the calculated value by the electrode area was defined as an oxygen reduction current density (mA / cm 2 ).
- the catalytic ability of the produced fuel cell electrode (1) was evaluated based on the oxygen reduction starting potential and the oxygen reduction current density.
- FIG. 2 shows a current-potential curve obtained by the above measurement.
- Catalyst (1) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.813 V and 0.513 mA / cm 2 .
- Example 2 Production of catalyst The same operation as in Example 1 was conducted except that a NAFION (registered trademark) solution was not used, to obtain 281 mg of a powdery catalyst (2). The weight of the powder for firing obtained in this process was 12.3 g.
- NAFION registered trademark
- the powder X-ray diffraction spectrum of the catalyst (2) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (2) (ratio of the number of atoms) and the BET specific surface area of the catalyst (2).
- a fuel cell electrode (2) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (2) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (2) had an oxygen reduction starting potential of 0.93 V (vs. RHE) and an oxygen reduction current density of 0.476 mA / cm 2 at 0.80 V.
- Example 3 Production of catalyst The same operation as in Example 1 was carried out except that iron (II) acetate was not used, to obtain 224 mg of a powdery catalyst (3). The weight of the powder for firing obtained in this process was 14.7 g.
- the powder X-ray diffraction spectrum of the catalyst (3) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (3) (ratio of the number of atoms) and the BET specific surface area of the catalyst (3).
- a fuel cell electrode (3) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (3) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (3) had an oxygen reduction starting potential of 0.85 V (vs. RHE) and an oxygen reduction current density of 0.016 mA / cm 2 at 0.80 V.
- Example 4 Production of catalyst The same operation as in Example 3 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 224 mg of a powdery catalyst (4). The weight of the powder for firing obtained in this process was 14.7 g.
- NAFION registered trademark
- Table 1 shows the ratio of each element constituting the catalyst (4) (the ratio of the number of atoms) and the BET specific surface area of the catalyst (4).
- a fuel cell electrode (4) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (4) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (4) had an oxygen reduction starting potential of 0.85 V (vs. RHE) and an oxygen reduction current density of 0.72 V and was 0.002 mA / cm 2 .
- Example 5 Production of catalyst 16 ml of acetic acid was placed in a beaker, and 5.58 g (17.59 mmol) of tin (II) acetylacetonate was added thereto while stirring to prepare a tin solution (5).
- Example 2 The same operation as in Example 1 was carried out except that the tin solution (5) was used instead of the tin solution (1) to obtain 212 mg of a powdery catalyst (5).
- the weight of the powder for firing obtained in this process was 10.9 g.
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (5) and the BET specific surface area of the catalyst (5).
- a fuel cell electrode (5) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (5) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (5) had an oxygen reduction starting potential of 0.94 V (vs. RHE) and an oxygen reduction current density of 1.070 mA / cm 2 at 0.80 V.
- Example 6 Production of catalyst 70 ml of acetic acid was placed in a beaker, and 5.58 g (17.59 mmol) of tin (II) acetylacetonate was added thereto while stirring to prepare a tin solution (6).
- Example 5 The same procedure as in Example 5 was performed except that the tin solution (6) was used instead of the tin solution (5) and the NAFION (registered trademark) solution was not used, and 327 mg of a powdery catalyst (6) Got.
- the weight of the powder for firing obtained in this process was 10.7 g.
- the powder X-ray diffraction spectrum of the catalyst (6) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (6) (ratio of the number of atoms) and the BET specific surface area of the catalyst (6).
- a fuel cell electrode (6) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (6) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (6) had an oxygen reduction starting potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.453 mA / cm 2 at 0.80 V.
- Example 7 Production of catalyst In a beaker, 25 ml of methanol was added, and while stirring, 5.33 g (20 mmol) of tin tetrachloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 355 mg (2.049 mmol) was added sequentially. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (7).
- NAFION® Nafion
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (7), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 8.12 g of powder for firing (7) was obtained.
- Example 2 The same operation as in Example 1 was performed except that the firing powder (1) was changed to the firing powder (7) (1.2 g) to obtain 320 mg of a powdery catalyst (7).
- Table 1 shows the ratio of each element constituting the catalyst (7) (ratio of the number of atoms) and the BET specific surface area of the catalyst (7).
- a fuel cell electrode (7) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (7) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (7) had an oxygen reduction starting potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.868 V and 0.368 mA / cm 2 .
- Example 8 Production of catalyst 33 ml of methanol was placed in a beaker, and 5.33 g (20 mmol) of tin tetrachloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (8).
- Example 7 The same operation as in Example 7 was performed except that the catalyst precursor solution (7) was changed to the catalyst precursor solution (8) to obtain 326 mg of a powdery catalyst (8).
- the weight of the powder for firing obtained in this process was 8.59 g.
- the powder X-ray diffraction spectrum of the catalyst (8) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (8) (ratio of the number of atoms) and the BET specific surface area of the catalyst (8).
- a fuel cell electrode (8) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (8) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (8) had an oxygen reduction initiation potential of 0.93 V (vs. RHE) and an oxygen reduction current density of 0.133 mA / cm 2 at 0.80 V.
- Example 9 Production of catalyst In a beaker, 50 ml of methanol was added, and while stirring, 2.75 g (20.45 mmol) of copper dichloride, 10 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 355 mg (2.045 mmol) was added sequentially. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (9).
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (9), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 3.56 g of powder for firing (9) was obtained.
- Example 2 The same operation as in Example 1 was carried out except that the firing powder (1) was changed to the firing powder (9) (1.2 g) to obtain 562 mg of a powdery catalyst (9).
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (9) and the BET specific surface area of the catalyst (9).
- a fuel cell electrode (9) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (9) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (9) had an oxygen reduction starting potential of 0.97 V (vs. RHE) and an oxygen reduction current density of 0.827 V and 2.027 mA / cm 2 .
- Example 10 Production of catalyst The same operation as in Example 9 was carried out except that tetraethylammonium tetrafluoroborate was used in place of the NAFION (registered trademark) solution to obtain 667 mg of a powdery catalyst (10). The weight of the powder for firing obtained in this process was 3.00 g.
- the powder X-ray diffraction spectrum of the catalyst (10) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (10) (ratio of the number of atoms) and the BET specific surface area of the catalyst (10).
- a fuel cell electrode (10) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (10) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (10) had an oxygen reduction initiation potential of 0.96 V (vs. RHE) and an oxygen reduction current density of 1.047 mA / cm 2 at 0.80 V.
- Example 11 Production of catalyst The same operation as in Example 9 was carried out except that tetramethylammonium hexafluorophosphate was used instead of the NAFION (registered trademark) solution to obtain 708 mg of a powdery catalyst (11). The weight of the powder for firing obtained in this process was 2.89 g.
- the powder X-ray diffraction spectrum of the catalyst (11) is shown in FIG.
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (11) and the BET specific surface area of the catalyst (11).
- a fuel cell electrode (11) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (11) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (11) had an oxygen reduction initiation potential of 0.93 V (vs. RHE) and an oxygen reduction current density of 0.949 mA / cm 2 at 0.80 V.
- Example 12 Production of catalyst The same operation as in Example 9 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 682 mg of a powdery catalyst (12). The weight of the powder for firing obtained in this process was 3.07 g.
- NAFION registered trademark
- Table 1 shows the ratio of each element constituting the catalyst (12) (ratio of the number of atoms) and the BET specific surface area of the catalyst (12).
- a fuel cell electrode (12) was produced in the same manner as in Example 1 except that 95 mg of catalyst (12) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (12) had an oxygen reduction starting potential of 0.92 V (vs. RHE) and an oxygen reduction current density of 1.362 mA / cm 2 at 0.80 V.
- Example 13 Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring this, 5.05 g (20.45 mmol) of cerium trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid 355 mg (2.045 mmol) of iron (II) was added sequentially. Pyrazinecarboxylic acid (10.15 g, 81.80 mmol) was added little by little to the resulting solution, followed by stirring for 3 hours to obtain a catalyst precursor solution (13).
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (13), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residue and the like were removed, and 9.72 g of powder for firing (13) was obtained.
- Example 2 The same operation as in Example 1 was carried out except that the firing powder (1) was changed to the firing powder (13) (1.2 g) to obtain 637 mg of a powdery catalyst (13).
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (13) and the BET specific surface area of the catalyst (13).
- a fuel cell electrode (13) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (13) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (13) had an oxygen reduction starting potential of 1.03 V (vs. RHE) and an oxygen reduction current density of 0.717 mA / cm 2 at 0.80 V.
- Example 14 Production of catalyst The same operation as in Example 13 was carried out except that the NAFION (registered trademark) solution was not used, to obtain 682 mg of a powdery catalyst (14). The weight of the powder for firing obtained in this process was 3.07 g.
- NAFION registered trademark
- the powder X-ray diffraction spectrum of the catalyst (14) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (14) (ratio of the number of atoms) and the BET specific surface area of the catalyst (14).
- a fuel cell electrode (14) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (14) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (14) had an oxygen reduction starting potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.218 mA / cm 2 at 0.80 V.
- Example 15 Preparation of catalyst In a beaker, 27 ml of methanol was added, and while stirring, 3.45 g (20.45 mmol) of aluminum trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid Iron (II) 357 mg (2.049 mmol) was sequentially added. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (15).
- NAFION® 5% Nafion
- II acetic acid Iron
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (15), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 6.40 g of powder for firing (15) was obtained.
- Example 2 The same operation as in Example 1 was performed except that the firing powder (1) was changed to the firing powder (15) (1.2 g) to obtain 452 mg of a powdery catalyst (15).
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (15) and the BET specific surface area of the catalyst (15).
- a fuel cell electrode (15) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (15) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Example 16 Production of catalyst 37 ml of methanol was placed in a beaker, and 3.45 g (20.45 mmol) of aluminum trichloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (16).
- Example 15 Except for changing the catalyst precursor solution (15) to the catalyst precursor solution (16), the same operation as in Example 15 was performed to obtain 646 mg of a powdery catalyst (16). In addition, the weight of the powder for baking obtained in this process was 5.73 g.
- Table 1 shows the ratio of each element constituting the catalyst (16) (ratio of the number of atoms) and the BET specific surface area of the catalyst (16).
- a fuel cell electrode (16) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (16) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (16) had an oxygen reduction starting potential of 0.83 V (vs. RHE) and an oxygen reduction current density of 0.80 V and 0.060 mA / cm 2 .
- Example 17 Preparation of catalyst In a beaker, 45 ml of methanol was added, and while stirring, 6.66 g (20.45 mmol) of tungsten tetrachloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid Iron (II) 355 mg (2.049 mmol) was sequentially added. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid little by little to the resulting solution, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (17).
- NAFION® Nafion
- II acetic acid Iron
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (17), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 6.34 g of powder for firing (17) was obtained.
- Example 2 The same operation as in Example 1 was performed except that the firing powder (1) was changed to the firing powder (17) (1.2 g) to obtain 305 mg of a powdery catalyst (17).
- Table 1 shows the ratio of each element constituting the catalyst (17) (ratio of the number of atoms) and the BET specific surface area of the catalyst (17).
- a fuel cell electrode (17) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (17) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (17) had an oxygen reduction starting potential of 0.83 V (vs. RHE) and an oxygen reduction current density of 0.012 mA / cm 2 at 0.80 V.
- Example 18 Production of catalyst 33 ml of methanol was placed in a beaker, and 6.66 g (20.45 mmol) of tungsten tetrachloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (18).
- Example 17 The same operation as in Example 17 was performed except that the catalyst precursor solution (17) was changed to the catalyst precursor solution (18) to obtain 699 mg of a powdery catalyst (18). In addition, the weight of the powder for baking obtained in this process was 8.29 g.
- Table 1 shows the ratio of each element constituting the catalyst (18) (ratio of the number of atoms) and the BET specific surface area of the catalyst (18).
- a fuel cell electrode (18) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (18) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (18) had an oxygen reduction starting potential of 0.78 V (vs. RHE) and an oxygen reduction current density of 0.004 mA / cm 2 at 0.80 V.
- Example 19 Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring this, 3.88 g (20.45 mmol) of yttrium trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid 355 mg (2.045 mmol) of iron (II) was added sequentially. Pyrazinecarboxylic acid (10.15 g, 81.80 mmol) was added little by little to the resulting solution, followed by stirring for 3 hours to obtain a catalyst precursor solution (19).
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (19), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 8.81 g of powder for firing (19) was obtained.
- Example 2 The same operation as in Example 1 was performed except that the firing powder (1) was changed to the firing powder (19) (1.2 g) to obtain 684 mg of a powdery catalyst (19).
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (19) and the BET specific surface area of the catalyst (19).
- a fuel cell electrode (19) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (19) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (19) had an oxygen reduction starting potential of 0.90 V (vs. RHE) and an oxygen reduction current density of 0.885 V and 0.385 mA / cm 2 .
- Example 20 Production of catalyst The same operation as in Example 19 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 597 mg of a powdery catalyst (20). The weight of the powder for firing obtained in this process was 9.61 g.
- NAFION registered trademark
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (20) and the BET specific surface area of the catalyst (20).
- a fuel cell electrode (20) was produced in the same manner as in Example 1 except that 95 mg of catalyst (20) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (20) had an oxygen reduction start potential of 0.92 V (vs. RHE) and an oxygen reduction current density of 0.134 mA / cm 2 at 0.80 V.
- Example 21 Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring, 5.31 g (20.45 mmol) of nickel dichloride, 25 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 710 mg (4.09 mmol) was added sequentially. After adding 20.30 g (163.6 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (21).
- NAFION® 5% Nafion
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (21), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, and 12.7 g of powder for firing (21) was obtained.
- Example 2 The same operation as in Example 1 was performed except that the firing powder (1) was changed to the firing powder (21) (1.2 g) to obtain 362 mg of a powdery catalyst (21).
- Table 1 shows the ratio of each element constituting the catalyst (21) (ratio of the number of atoms) and the BET specific surface area of the catalyst (21).
- a fuel cell electrode (21) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (21) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- Catalyst (21) had an oxygen reduction starting potential of 0.87 V (vs. RHE) and an oxygen reduction current density of 0.025 mA / cm 2 at 0.80 V.
- Example 22 Production of catalyst 100 ml of methanol was put into a beaker, and 5.30 g (40.90 mmol) of nickel dichloride and 710 mg (4.09 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 20.30 g (163.6 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, stirring was performed for 3 hours to obtain a catalyst precursor solution (22).
- Example 21 The same operation as in Example 21 was performed except that the catalyst precursor solution (21) was changed to the catalyst precursor solution (22) to obtain 459 mg of a powdery catalyst (22).
- the weight of the powder for firing obtained in this process was 12.3 g.
- the powder X-ray diffraction spectrum of the catalyst (22) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (22) (the ratio of the number of atoms) and the BET specific surface area of the catalyst (22).
- a fuel cell electrode (22) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (22) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (22) had an oxygen reduction starting potential of 0.86 V (vs. RHE) and an oxygen reduction current density of 0.016 mA / cm 2 at 0.80 V.
- Example 23 Production of catalyst Into a beaker, 58 ml of acetic acid was added, and 6.14 g (17.54 mmol) of chromium (III) acetylacetonate was added with stirring to prepare a chromium solution (23).
- Example 2 The same operation as in Example 1 was carried out except that the chromium solution (23) was used instead of the tin solution (1) to obtain 257 mg of a powdery catalyst (23).
- the weight of the powder for firing obtained in this process was 14.7 g.
- Table 1 shows the ratio (number of atoms) of each element constituting the catalyst (23) and the BET specific surface area of the catalyst (23).
- a fuel cell electrode (23) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (23) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (23) had an oxygen reduction start potential of 1.01 V (vs. RHE) and an oxygen reduction current density of 0.337 mA / cm 2 at 0.80 V.
- Example 24 Production of catalyst The same operation as in Example 23 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 262 mg of a powdery catalyst (24). The weight of the powder for firing obtained in this process was 13.4 g.
- NAFION registered trademark
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (24) and the BET specific surface area of the catalyst (24).
- a fuel cell electrode (24) was produced in the same manner as in Example 1 except that 95 mg of catalyst (24) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (24) had an oxygen reduction starting potential of 0.85 V (vs. RHE) and an oxygen reduction current density of 0.076 mA / cm 2 at 0.80 V.
- Example 25 Production of catalyst Into a beaker, 58 ml of acetic acid was added, and 6.21 g (17.59 mmol) of iron (III) acetylacetonate was added with stirring to prepare an iron solution (25).
- Example 2 The same operation as in Example 1 was performed except that the iron solution (25) was used in place of the tin solution (1) to obtain 225 mg of a powdery catalyst (25).
- the weight of the powder for firing obtained in this process was 14.7 g.
- Table 1 shows the ratio of each element constituting the catalyst (25) (ratio of the number of atoms) and the BET specific surface area of the catalyst (25).
- a fuel cell electrode (25) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (25) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (25) had an oxygen reduction starting potential of 0.93 V (vs. RHE) and an oxygen reduction current density of 0.634 mA / cm 2 at 0.80 V.
- Example 26 Production of catalyst The same operation as in Example 25 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 262 mg of a powdery catalyst (26). The weight of the powder for firing obtained in this process was 10.6 g.
- NAFION registered trademark
- Table 1 shows the ratio of each element constituting the catalyst (26) (the ratio of the number of atoms) and the BET specific surface area of the catalyst (26).
- a fuel cell electrode (26) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (26) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (26) had an oxygen reduction initiation potential of 0.92 V (vs. RHE) and an oxygen reduction current density of 0.279 mA / cm 2 at 0.80 V.
- Example 27 Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 5.16 g (17.59 mmol) of cobalt (II) acetylacetonate hydrate was added thereto while stirring to prepare a cobalt solution (27).
- Example 2 The same operation as in Example 1 was performed except that the cobalt solution (27) was used instead of the tin solution (1) to obtain 356 mg of a powdery catalyst (27).
- the weight of the powder for firing obtained in this process was 19.2 g.
- Table 1 shows the ratio (ratio of the number of atoms) of each element constituting the catalyst (27) and the BET specific surface area of the catalyst (27).
- a fuel cell electrode (27) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (27) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (27) had an oxygen reduction initiation potential of 0.94 V (vs. RHE) and an oxygen reduction current density of 0.096 mA / cm 2 at 0.80 V.
- Example 28 Production of catalyst The same operation as in Example 27 was carried out except that the NAFION (registered trademark) solution was not used, to obtain 306 mg of a powdery catalyst (28). In addition, the weight of the powder for baking obtained in this process was 10.3 g.
- NAFION registered trademark
- Table 1 shows the ratio of each element constituting the catalyst (28) (ratio of the number of atoms) and the BET specific surface area of the catalyst (28).
- a fuel cell electrode (28) was produced in the same manner as in Example 1 except that 95 mg of catalyst (28) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (28) had an oxygen reduction initiation potential of 0.89 V (vs. RHE) and an oxygen reduction current density of 0.083 mA / cm 2 at 0.80 V.
- Example 29 1. Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 6.20 g (17.59 mmol) of manganese (III) acetylacetonate was added with stirring to prepare a manganese solution (29).
- Example 2 The same operation as in Example 1 was carried out except that the manganese solution (29) was used instead of the tin solution (1) to obtain 292 mg of a powdery catalyst (29).
- the weight of the powder for firing obtained in this process was 10.5 g.
- Table 1 shows the ratio of each element constituting the catalyst (29) (the ratio of the number of atoms) and the BET specific surface area of the catalyst (29).
- a fuel cell electrode (29) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (29) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (29) had an oxygen reduction starting potential of 1.02 V (vs. RHE) and an oxygen reduction current density of 0.155 mA / cm 2 at 0.80 V.
- Example 30 Production of catalyst The same operation as in Example 29 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 315 mg of a powdery catalyst (30). The weight of the powder for firing obtained in this process was 9.76 g.
- NAFION registered trademark
- Table 1 shows the ratio of each element constituting the catalyst (30) (ratio of the number of atoms) and the BET specific surface area of the catalyst (30).
- a fuel cell electrode (30) was produced in the same manner as in Example 1 except that 95 mg of catalyst (30) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (30) had an oxygen reduction starting potential of 0.87 V (vs. RHE) and an oxygen reduction current density of 0.052 mA / cm 2 at 0.80 V.
- Example 31 Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 5.03 g (17.59 mmol) of strontium bisacetylacetonate was added with stirring to prepare a strontium solution (31).
- Example 2 The same operation as in Example 1 was carried out except that the strontium solution (31) was used instead of the tin solution (1) to obtain 340 mg of a powdery catalyst (31).
- the weight of the powder for firing obtained in this process was 10.6 g.
- the powder X-ray diffraction spectrum of the catalyst (31) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (31) (ratio of the number of atoms) and the BET specific surface area of the catalyst (31).
- a fuel cell electrode (31) was produced in the same manner as in Example 1 except that 95 mg of catalyst (31) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (31) had an oxygen reduction start potential of 1.03 V (vs. RHE) and an oxygen reduction current density of 0.061 mA / cm 2 at 0.80 V.
- Example 32 Production of catalyst The same operation as in Example 31 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 337 mg of a powdery catalyst (32). The weight of the powder for firing obtained in this process was 10.0 g.
- NAFION registered trademark
- the powder X-ray diffraction spectrum of the catalyst (32) is shown in FIG.
- Table 1 shows the ratio of each element constituting the catalyst (32) (ratio of the number of atoms) and the BET specific surface area of the catalyst (32).
- a fuel cell electrode (32) was produced in the same manner as in Example 1 except that 95 mg of catalyst (32) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (32) had an oxygen reduction starting potential of 0.90 V (vs. RHE) and an oxygen reduction current density of 0.038 mA / cm 2 at 0.80 V.
- Example 33 Preparation of catalyst In a beaker, 100 ml of methanol was added, and while stirring, 5.50 g (40.9 mmol) of copper dichloride, 25 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 711 mg (4.09 mmol) was added sequentially. To the obtained solution, 15.23 g (121.6 mmol) of pyrazinecarboxylic acid was added little by little, followed by stirring for 3 hours to obtain a catalyst precursor solution (33). During this stirring, a precipitate was formed over time.
- NAFION® Nafion
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, the solvent was slowly evaporated while heating and stirring the catalyst precursor solution (33), and further under a nitrogen stream, By heating at 300 ° C. for 1 hour, chloride residues and the like were removed, allowed to cool to room temperature, and then ground in an automatic mortar for 30 minutes to obtain 6.52 g of powder for firing (33).
- Table 1 shows the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (33) and the BET specific surface area of the catalyst (33).
- a fuel cell electrode (33) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (33) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (33) had an oxygen reduction starting potential of 0.97 V (vs. RHE) and an oxygen reduction current density of 2.088 mA / cm 2 at 0.80 V.
- Example 34 2 g of the powder for firing (33) was heated to 1050 ° C. at a heating rate of 10 ° C./min while flowing nitrogen gas containing 4% by volume of hydrogen gas at a rate of 125 ml / min in a rotary kiln furnace. By baking for 1.5 hours and naturally cooling, 778 mg of a powdery catalyst (34) was obtained.
- the powder X-ray diffraction spectrum of the catalyst (34) is shown in FIG.
- Table 1 shows the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (34) and the BET specific surface area of the catalyst (34).
- a fuel cell electrode (34) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (34) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (34) had an oxygen reduction starting potential of 0.90 V (vs. RHE) and an oxygen reduction current density of 0.246 mA / cm 2 at 0.80 V.
- Example 35 1. Production of catalyst 1.37 g (10.2 mmol) of copper dichloride and 1.94 g (10.2 mmol) of tin trichloride were used instead of copper chloride, and a 5% NAFION (registered trademark) solution (DE521, DuPont) ) was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 337 mg of a powdery catalyst (35). In addition, the weight of the powder for baking obtained in this process was 4.68 g.
- NAFION registered trademark
- the powder X-ray diffraction spectrum of the catalyst (35) is shown in FIG.
- a fuel cell electrode (35) was produced in the same manner as in Example 1 except that 95 mg of catalyst (35) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (35) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 1.314 mA / cm 2 at 0.80 V.
- Example 36 1. Production of catalyst The same procedure as in Example 35 was performed, except that the amount of copper dichloride was changed to 1.81 g (13.5 mmol) and the amount of tin trichloride was changed to 1.28 g (6.75 mmol). 327 mg of a powdery catalyst (36) was obtained. In addition, the weight of the powder for baking obtained in this process was 3.73g.
- the powder X-ray diffraction spectrum of the catalyst (36) is shown in FIG.
- a fuel cell electrode (36) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (36) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (36) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 1.280 mA / cm 2 at 0.80 V.
- Example 37 Production of catalyst The same operation as in Example 35 was performed except that the amount of copper dichloride was changed to 0.907 g (6.75 mmol) and the amount of tin trichloride was changed to 2.56 g (13.5 mmol). 275 mg of a powdery catalyst (37) was obtained. The weight of the powder for firing obtained in this process was 5.10 g.
- the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (37) and the BET specific surface area of the catalyst (37) are shown in Table 1-1.
- a fuel cell electrode (37) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (37) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (37) had an oxygen reduction initiation potential of 0.96 V (vs. RHE) and an oxygen reduction current density of 1.224 mA / cm 2 at 0.80 V.
- Example 38 1. Production of catalyst Using 1.37 g (10.2 mmol) of copper dichloride and 1.94 g (10.2 mmol) of titanium tetrachloride instead of copper chloride, a 5% NAFION (registered trademark) solution (DE521, DuPont) ) was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 426 mg of a powdery catalyst (38). The weight of the powder for firing (33) obtained in this process was 3.52 g.
- NAFION registered trademark
- FIG. 75 shows the powder X-ray diffraction spectrum of the catalyst (38).
- a fuel cell electrode (38) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (38) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (38) had an oxygen reduction starting potential of 1.00 V (vs. RHE) and an oxygen reduction current density of 1.201 mA / cm 2 at 0.80 V.
- Example 39 1. Production of catalyst The same operation as in Example 38 was performed except that the amount of titanium tetrachloride was changed to 1.28 g (6.75 mmol) and the amount of copper dichloride was changed to 1.81 g (13.5 mmol). 425 mg of a powdery catalyst (39) was obtained. The weight of the firing powder (39) obtained in this process was 3.57 g.
- the powder X-ray diffraction spectrum of the catalyst (39) is shown in FIG.
- the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (39) and the BET specific surface area of the catalyst (39) are shown in Table 1-1.
- a fuel cell electrode (39) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (39) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (39) had an oxygen reduction starting potential of 1.00 V (vs. RHE) and an oxygen reduction current density of 1.345 mA / cm 2 at 0.80 V.
- Example 40 Production of Catalyst The same operation as in the production process of the firing powder (39) in Example 39 was performed to obtain 3.57 g of the firing powder (40).
- the powder X-ray diffraction spectrum of the catalyst (40) is shown in FIG.
- Table 1-1 shows the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (40) and the BET specific surface area of the catalyst (40).
- a fuel cell electrode (40) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (40) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (40) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 1.328 mA / cm 2 at 0.80 V.
- Example 41 Production of catalyst The same operation as in Example 38 was performed except that the amount of titanium tetrachloride was changed to 0.388 g (2.04 mmol) and the amount of copper dichloride was changed to 0.475 g (18.4 mmol). 313 mg of a powdery catalyst (41) was obtained. The weight of the firing powder (41) obtained in this process was 3.39 g.
- a fuel cell electrode (41) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (41) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (41) had an oxygen reduction starting potential of 0.98 V (vs. RHE) and an oxygen reduction current density of 1.530 mA / cm 2 at 0.80 V.
- Example 42 Into a beaker, 8 ml of acetic acid was added, and 2.60 g (25.9 mmol) of acetylacetone and 7.94 g (17.6 mmol) of zirconia butoxide were added with stirring to prepare a zirconium solution (42).
- Solution B was added dropwise to Solution A, followed by stirring for 3 hours to obtain a catalyst precursor solution (42).
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, and the solvent was slowly evaporated while heating and stirring the catalyst precursor solution.
- the solid residue obtained by completely evaporating the solvent was ground in an automatic mortar for 30 minutes to obtain 7.79 g of a powder for firing (42).
- Example 2 The same operation as in Example 1 was carried out except that the firing powder (1) was changed to the firing powder (42) (1.2 g) to obtain 641 mg of a powdery catalyst (42).
- a fuel cell electrode (42) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (42) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (42) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.957 mA / cm 2 at 0.80 V.
- Example 43 8 ml of acetic acid was put into a beaker, and 1.30 g (13.0 mmol) of acetylacetone and 3.92 g (10.2 mmol) of zirconia butoxide were added while stirring the mixture to prepare a zirconium solution (43).
- Solution B was added dropwise to Solution A, followed by stirring for 3 hours to obtain a catalyst precursor solution (43). During the stirring for 3 hours, a precipitate was deposited with the passage of time.
- Example 42 The same operation as in Example 42 was performed except that the catalyst precursor solution (42) was changed to the catalyst precursor solution (43), to obtain 624 mg of a powdery catalyst (43).
- the weight of the firing powder (43) obtained in this process was 5.34 g.
- the ratio of each metal element constituting the catalyst (43) (ratio of the number of atoms) and the BET specific surface area of the catalyst (43) are shown in Table 1-1.
- a fuel cell electrode (43) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (43) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (43) had an oxygen reduction initiation potential of 0.94 V (vs. RHE) and an oxygen reduction current density of 1.298 mA / cm 2 at 0.80 V.
- Example 44 1. Preparation of catalyst 5% Nafion (registered trademark) solution (DE521, DuPont) using 1.94 g (10.2 mmol) of titanium tetrachloride and 1.94 g (10.2 mmol) of tin trichloride instead of copper chloride ) was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 358 mg of a powdery catalyst (44). The weight of the firing powder (44) obtained in this process was 5.00 g.
- a fuel cell electrode (44) was produced in the same manner as in Example 1 except that 95 mg of catalyst (44) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (44) had an oxygen reduction start potential of 1.00 V (vs. RHE) and an oxygen reduction current density of 0.631 mA / cm 2 at 0.80 V.
- Example 45 1. Preparation of catalyst 1.37 g (10.2 mmol) of copper dichloride and 5.66 g (10.2 mmol) of tantalum pentachloride were used instead of copper chloride, and a 5% NAFION (registered trademark) solution (DE521, DuPont) ) was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 714 mg of a powdery catalyst (45). The weight of the firing powder obtained in this process was 7.16 g.
- NAFION registered trademark
- the powder X-ray diffraction spectrum of the catalyst (45) is shown in FIG.
- the ratio (ratio of the number of atoms) of each metal element constituting the catalyst (45) and the BET specific surface area of the catalyst (45) are shown in Table 1-1.
- a fuel cell electrode (45) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (45) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (45) had an oxygen reduction initiation potential of 0.95 V (vs. RHE) and an oxygen reduction current density of 0.628 mA / cm 2 at 0.80 V.
- Example 46 1. Production of catalyst The same procedure as in Example 45 was performed, except that the amount of copper dichloride was changed to 1.81 g (13.5 mmol) and the amount of tantalum pentachloride was changed to 2.42 g (6.45 mmol). 628 mg of a powdery catalyst (46) was obtained. The weight of the powder for firing (46) obtained in this process was 4.27 g.
- a fuel cell electrode (46) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (46) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (46) had an oxygen reduction starting potential of 0.93 V (vs. RHE) and an oxygen reduction current density of 0.884 V / 0.884 mA / cm 2 .
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, and the solvent was slowly evaporated while heating and stirring the catalyst precursor solution.
- the solid residue obtained by completely evaporating the solvent was finely and uniformly crushed with a mortar to obtain a powder for firing.
- This powder is put into a tubular furnace, heated to 890 ° C. at a temperature rising rate of 10 ° C./min in an atmosphere of nitrogen gas containing 4% by volume of hydrogen gas, held at 890 ° C. for 1 hour, and naturally cooled to form powder.
- Catalyst (c1) was obtained.
- the BET specific surface area of the catalyst (c1) was 77 m 2 / g.
- Fuel Cell Electrode (c1) by the same method as in Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (c1) had an oxygen reduction starting potential of 0.62 V (vs. RHE) and an oxygen reduction current density of 0.000 mA / cm 2 at 0.80 V.
- the BET specific surface area of the catalyst (c2) was 3.6 m 2 / g.
- Electrode for fuel cell (c2) by the same method as Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (c2) had an oxygen reduction starting potential of 0.64 V (vs. RHE) and an oxygen reduction current density of 0.80 V and 0.000 mA / cm 2 .
- the BET specific surface area of the catalyst (c3) was 229 m 2 / g.
- the measurement results are shown in FIG.
- the catalyst (c3) had an oxygen reduction starting potential of 0.76 V (vs. RHE) and an oxygen reduction current density of 0.000 mA / cm 2 at 0.80 V.
- the BET specific surface area of the catalyst (c4) was 9.4 m 2 / g.
- Electrode for fuel cell (c4) by the same method as in Example 1 except that 0.095 g of catalyst (c4) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
- the measurement results are shown in FIG.
- the catalyst (c4) had an oxygen reduction starting potential of 0.47 V (vs. RHE) and an oxygen reduction current density of 0.000 mA / cm 2 at 0.80 V.
- the BET specific surface area of the catalyst (c5) was 1.8 m 2 / g.
- the measurement results are shown in FIG.
- the catalyst (c5) had an oxygen reduction starting potential of 0.55 V (vs. RHE) and an oxygen reduction current density of 0.000 mA / cm 2 at 0.80 V.
Abstract
Description
少なくとも金属化合物(1)と、窒素含有有機化合物(2)と、溶媒とを混合して触媒前駆体溶液を得る工程(1)、
前記触媒前駆体溶液から溶媒を除去する工程(2)、および
工程(2)で得られた固形分残渣を500~1100℃の温度で熱処理して電極触媒を得る工程(3)
を含み、
前記金属化合物(1)の一部または全部が、金属元素としてアルミニウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、ストロンチウム、イットリウム、スズ、タングステンおよびセリウムから選ばれる金属元素M1を含有する化合物であり、
前記工程(1)で用いられる成分のうち溶媒以外の少なくとも1つの成分が酸素原子を有する
ことを特徴とする燃料電池用電極触媒の製造方法。 [1]
A step (1) of obtaining a catalyst precursor solution by mixing at least a metal compound (1), a nitrogen-containing organic compound (2), and a solvent;
Step (2) for removing the solvent from the catalyst precursor solution, and Step (3) for obtaining an electrode catalyst by heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
Including
A part or all of the metal compound (1) is a compound containing a metal element M1 selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten and cerium as a metal element. Yes,
A method for producing an electrode catalyst for a fuel cell, wherein at least one component other than the solvent among the components used in the step (1) has an oxygen atom.
前記工程(1)において、ホウ素、リンおよび硫黄からなる群から選ばれる少なくとも1種の元素Aならびにフッ素を含有する化合物(3)をさらに混合することを特徴とする請求項1に記載の燃料電池用電極触媒の製造方法。 [2]
2. The fuel cell according to
前記化合物(3)が、フッ素を含有するホウ酸誘導体、フッ素を含有するスルホン酸誘導体およびフッ素を含有するリン酸誘導体からなる群から選ばれる少なくとも1種であることを特徴とする上記[2]に記載の燃料電池用電極触媒の製造方法。 [3]
The compound [3] is at least one selected from the group consisting of a boric acid derivative containing fluorine, a sulfonic acid derivative containing fluorine, and a phosphoric acid derivative containing fluorine [2] The manufacturing method of the electrode catalyst for fuel cells of description.
前記工程(1)において、前記金属化合物(1)の溶液と、前記窒素含有有機化合物(2)とを混合することを特徴とする上記[1]~[3]のいずれかに記載の燃料電池用電極触媒の製造方法。 [4]
The fuel cell according to any one of [1] to [3], wherein in the step (1), the solution of the metal compound (1) and the nitrogen-containing organic compound (2) are mixed. For producing an electrode catalyst.
前記工程(1)において、ジケトン構造を有する化合物からなる沈殿抑制剤をさらに混合することを特徴とする上記[1]~[4]のいずれかに記載の燃料電池用電極触媒の製造方法。 [5]
The method for producing a fuel cell electrode catalyst according to any one of the above [1] to [4], wherein in the step (1), a precipitation inhibitor comprising a compound having a diketone structure is further mixed.
前記金属化合物(1)が、金属リン酸塩、金属硫酸塩、金属硝酸塩、金属有機酸塩、金属酸ハロゲン化物、金属アルコキシド、金属ハロゲン化物、金属過ハロゲン酸塩、金属次亜ハロゲン酸塩および金属錯体からなる群から選ばれる少なくとも1種であることを特徴とする上記[1]~[5]のいずれかに記載の燃料電池用電極触媒の製造方法。 [6]
The metal compound (1) is a metal phosphate, metal sulfate, metal nitrate, metal organic acid salt, metal acid halide, metal alkoxide, metal halide, metal perhalogenate, metal hypohalite and The method for producing an electrode catalyst for a fuel cell according to any one of the above [1] to [5], wherein the method is at least one selected from the group consisting of metal complexes.
前記窒素含有有機化合物(2)が、アミノ基、ニトリル基、イミド基、イミン基、ニトロ基、アミド基、アジド基、アジリジン基、アゾ基、イソシアネート基、イソチオシアネート基、オキシム基、ジアゾ基、およびニトロソ基、ならびにピロール環、ポルフィリン環、イミダゾール環、ピリジン環、ピリミジン環、およびピラジン環から選ばれる1種類以上を分子中に有することを特徴とする上記[1]~[6]のいずれかに記載の燃料電池用電極触媒の製造方法。 [7]
The nitrogen-containing organic compound (2) is an amino group, nitrile group, imide group, imine group, nitro group, amide group, azide group, aziridine group, azo group, isocyanate group, isothiocyanate group, oxime group, diazo group, And any one of the above-mentioned [1] to [6], wherein the molecule has at least one selected from the group consisting of a pyrrole ring, a porphyrin ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. The manufacturing method of the electrode catalyst for fuel cells of description.
前記窒素含有有機化合物(2)が、水酸基、カルボキシル基、アルデヒド基、酸ハライド基、スルホ基、リン酸基、ケトン基、エーテル基、およびエステル基から選ばれる1種類以上を分子中に有することを特徴とする上記[1]~[7]のいずれかに記載の燃料電池用電極触媒の製造方法。 [8]
The nitrogen-containing organic compound (2) has one or more kinds selected from a hydroxyl group, a carboxyl group, an aldehyde group, an acid halide group, a sulfo group, a phosphoric acid group, a ketone group, an ether group, and an ester group in the molecule. The method for producing a fuel cell electrode catalyst according to any one of the above [1] to [7].
前記工程(3)において、前記固形分残渣を、水素ガスを0.01体積%以上10体積%以下含む雰囲気中で熱処理することを特徴とする上記[1]~[8]のいずれかに記載の燃料電池用電極触媒の製造方法。 [9]
In any one of the above [1] to [8], in the step (3), the solid residue is heat-treated in an atmosphere containing 0.01% by volume to 10% by volume of hydrogen gas. Of manufacturing an electrode catalyst for a fuel cell.
上記[1]~[9]のいずれかに記載の製造方法で得られる燃料電池用電極触媒。 [10]
A fuel cell electrode catalyst obtained by the production method according to any one of [1] to [9] above.
上記[10]に記載の燃料電池用電極触媒を含むことを特徴とする燃料電池用触媒層。 [11]
A fuel cell catalyst layer comprising the fuel cell electrode catalyst according to [10] above.
上記[11]に記載の燃料電池用触媒層と多孔質支持層とを有することを特徴とする電極。 [12]
An electrode comprising the fuel cell catalyst layer according to the above [11] and a porous support layer.
カソードとアノードと前記カソードおよび前記アノードの間に配置された電解質膜とを有する膜電極接合体であって、前記カソードおよび/または前記アノードが上記[12]に記載の電極であることを特徴とする膜電極接合体。 [13]
A membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is an electrode according to the above [12] Membrane electrode assembly.
上記[13]に記載の膜電極接合体を備えることを特徴とする燃料電池。 [14]
A fuel cell comprising the membrane electrode assembly according to the above [13].
固体高分子型燃料電池であることを特徴とする上記[14]に記載の燃料電池。 [15]
The fuel cell as described in [14] above, which is a polymer electrolyte fuel cell.
発電機能、発光機能、発熱機能、音響発生機能、運動機能、表示機能および充電機能からなる群より選ばれる少なくとも一つの機能を有する物品であって、上記[14]または[15]に記載の燃料電池を備えることを特徴とする物品。 [16]
An article having at least one function selected from the group consisting of a power generation function, a light emission function, a heat generation function, a sound generation function, a movement function, a display function, and a charging function, and the fuel according to [14] or [15] An article comprising a battery.
本発明の燃料電池用電極触媒の製造方法は、
少なくとも金属化合物(1)と、窒素含有有機化合物(2)と、溶媒とを混合して溶液(本明細書において「触媒前駆体溶液」とも記す。)を得る工程(1)、
前記触媒前駆体溶液から溶媒を除去する工程(2)、および
工程(2)で得られた固形分残渣を500~1100℃の温度で熱処理して電極触媒を得る工程(3)
を含み、
前記金属化合物(1)の一部または全部が、特定の金属元素M1を含有する金属化合物(M1)であり、
前記工程(1)で用いられる成分のうち溶媒以外の少なくとも1つの成分が酸素原子を有する(すなわち、後述する化合物(3)を用いる場合には、化合物(1)、化合物(2)および化合物(3)の少なくとも1つが酸素原子を有し、化合物(3)を用いない場合には、化合物(1)および化合物(2)の少なくとも1つが酸素原子を有する)ことを特徴としている。なお本明細書において、特段の事情がない限り、原子およびイオンを、厳密に区別することなく「原子」と記載する。 [Method for producing electrode catalyst for fuel cell]
The method for producing the fuel cell electrode catalyst of the present invention comprises:
A step (1) of obtaining a solution (also referred to as “catalyst precursor solution” in this specification) by mixing at least the metal compound (1), the nitrogen-containing organic compound (2), and a solvent;
Step (2) for removing the solvent from the catalyst precursor solution, and Step (3) for obtaining an electrode catalyst by heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
Including
A part or all of the metal compound (1) is a metal compound (M1) containing a specific metal element M1,
Among the components used in the step (1), at least one component other than the solvent has an oxygen atom (that is, when using the compound (3) described later, the compound (1), the compound (2) and the compound ( At least one of 3) has an oxygen atom, and when the compound (3) is not used, at least one of the compound (1) and the compound (2) has an oxygen atom). In the present specification, unless otherwise specified, atoms and ions are described as “atoms” without strictly distinguishing them.
工程(1)では、少なくとも金属化合物(1)と、窒素含有有機化合物(2)と、溶媒と、任意に後述する化合物(3)を混合して触媒前駆体溶液を得る。 (Process (1))
In step (1), at least a metal compound (1), a nitrogen-containing organic compound (2), a solvent, and optionally a compound (3) described later are mixed to obtain a catalyst precursor solution.
手順(i):1つの容器に溶媒を準備し、そこへ前記金属化合物(1)前記窒素含有有機化合物(2)および任意に前記化合物(3)を添加し、溶解させて、これらを混合する、
手順(ii):前記金属化合物(1)の溶液、ならびに前記窒素含有有機化合物(2)および任意に前記化合物(3)の溶液を準備し、これらを混合する
が挙げられる。 As the mixing procedure, for example,
Procedure (i): Prepare a solvent in one container, add the metal compound (1), the nitrogen-containing organic compound (2) and optionally the compound (3) to it, dissolve them, and mix them ,
Step (ii): preparing a solution of the metal compound (1) and a solution of the nitrogen-containing organic compound (2) and optionally the compound (3) and mixing them.
手順(ii'):前記金属化合物(M1)(ただし、遷移金属化合物(M12)を除く。)の溶液、ならびに前記遷移金属化合物(M12)、前記窒素含有有機化合物(2)および任意に前記化合物(3)の溶液を準備し、これらを混合する
が挙げられる。 As a preferable procedure in the procedure (ii) when using a transition metal compound (M12) described later as the metal compound (1),
Procedure (ii ′): a solution of the metal compound (M1) (excluding the transition metal compound (M12)), the transition metal compound (M12), the nitrogen-containing organic compound (2) and optionally the compound Prepare the solution of (3) and mix these.
前記金属化合物(1)の一部または全部は、以下の金属元素M1を含有する金属化合物(M1)である。金属元素M1は、具体的にはアルミニウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、ストロンチウム、イットリウム、スズ、タングステンおよびセリウムから選ばれる金属元素である。金属元素M1の中でも、アルミニウム、クロム、鉄、コバルト、銅、イットリウム、スズおよびセリウムが好ましく、銅が特に好ましい。これらは、1種単独で用いてもよく2種以上を併用してもよい。 <Metal compound (1)>
Part or all of the metal compound (1) is a metal compound (M1) containing the following metal element M1. Specifically, the metal element M1 is a metal element selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten, and cerium. Among the metal elements M1, aluminum, chromium, iron, cobalt, copper, yttrium, tin and cerium are preferable, and copper is particularly preferable. These may be used alone or in combination of two or more.
クロム(III)メトキシド、クロム(III)エトキシド、クロム(III)プロポキシド、クロム(III)イソプロポキシド、クロム(III)ブトキシド、クロム(III)イソブトキシド、クロム(III)ペントキシド、クロム(III)アセチルアセトナート、クロム(III)イソプロポキシドアセチルアセトナート(Cr(acac)(O-iPr)2、Cr(acac)2(O-iPr)、acacはアセチルアセトナトイオンを、iPrはイソプロピル基を表す。以下も同様である。)、トリスジエチルアミノクロム、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)クロム、クロム(III)ヘキサフルオロアセチルアセトナート、トリ-1-メトキシ-2-メチル-2-プロポキシクロム(III)、三塩化クロム、二塩化クロム、オキシ塩化クロム、三臭化クロム、二臭化クロム、オキシ臭化クロム、三ヨウ化クロム、二ヨウ化クロム、オキシヨウ化クロム等のクロム化合物;
マンガン(III)メトキシド、マンガン(III)エトキシド、マンガン(III)プロポキシド、マンガン(III)イソプロポキシド、マンガン(III)ブトキシド、マンガン(III)イソブトキシド、マンガン(III)ペントキシド、マンガン(III)アセチルアセトナート、マンガン(III)イソプロポキシドアセチルアセトナート(Mn(acac)(O-iPr)2、Mn(acac)2(O-iPr))、トリスジエチルアミノマンガン、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)マンガン、マンガン(III)ヘキサフルオロアセチルアセトナート、トリ-1-メトキシ-2-メチル-2-プロポキシマンガン(III)、三塩化マンガン、二塩化マンガン、オキシ塩化マンガン、三臭化マンガン、二臭化マンガン、オキシ臭化マンガン、三ヨウ化マンガン、二ヨウ化マンガン、オキシヨウ化マンガン等のマンガン化合物;
鉄(III)メトキシド、鉄(III)エトキシド、鉄(III)プロポキシド、鉄(III)イソプロポキシド、鉄(III)ブトキシド、鉄(III)イソブトキシド、鉄(III)ペントキシド、鉄(III)アセチルアセトナート、鉄(III)イソプロポキシドアセチルアセトナート(Fe(acac)(O-iPr)2、Fe(acac)2(O-iPr))、トリスジエチルアミノ鉄、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)鉄、鉄(III)ヘキサフルオロアセチルアセトナート、トリ-1-メトキシ-2-メチル-2-プロポキシ鉄(III)、三塩化鉄、二塩化鉄、オキシ塩化鉄、三臭化鉄、二臭化鉄、オキシ臭化鉄、三ヨウ化鉄、二ヨウ化鉄、オキシヨウ化鉄等の鉄化合物;
コバルト(II)メトキシド、コバルト(II)エトキシド、コバルト(II)プロポキシド、コバルト(II)イソプロポキシド、コバルト(II)ブトキシド、コバルト(II)イソブトキシド、コバルト(II)ペントキシド、コバルト(II)アセチルアセトナート、コバルト(III)アセチルアセトナート、コバルト(II)イソプロポキシドアセチルアセトナート(Co(acac)(O-iPr))、コバルト(III)イソプロポキシドアセチルアセトナート(Co(acac)(O-iPr)2、Co(acac)2(O-iPr))、ビスジエチルアミノコバルト、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)コバルト、コバルト(II)ヘキサフルオロアセチルアセトナート、トリ-1-メトキシ-2-メチル-2-プロポキシコバルト(II)、三塩化コバルト、二塩化コバルト、オキシ塩化コバルト、三臭化コバルト、二臭化コバルト、オキシ臭化コバルト、三ヨウ化コバルト、二ヨウ化コバルト、オキシヨウ化コバルト等のコバルト化合物;
ニッケル(II)メトキシド、ニッケル(II)エトキシド、ニッケル(II)プロポキシド、ニッケル(II)イソプロポキシド、ニッケル(II)ブトキシド、ニッケル(II)イソブトキシド、ニッケル(II)ペントキシド、ニッケル(II)アセチルアセトナート、ニッケル(II)イソプロポキシドアセチルアセトナート(Ni(acac)(O-iPr))、ビスジエチルアミノニッケル、ビス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)ニッケル、ニッケル(II)ヘキサフルオロアセチルアセトナート、ビス-1-メトキシ-2-メチル-2-プロポキシニッケル(II)、二塩化ニッケル、オキシ塩化ニッケル、二臭化ニッケル、オキシ臭化ニッケル、二ヨウ化ニッケル、オキシヨウ化ニッケル等のニッケル化合物;
銅(II)メトキシド、銅(II)エトキシド、銅(II)プロポキシド、銅(II)イソプロポキシド、銅(II)ブトキシド、銅(II)イソブトキシド、銅(II)ペントキシド、銅(II)アセチルアセトナート、ビスジエチルアミノ銅、ビス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)銅、銅(II)ヘキサフルオロアセチルアセトナート、ビス-1-メトキシ-2-メチル-2-プロポキシ銅(II)、二塩化銅、オキシ塩化銅、二臭化銅、オキシ臭化銅、二ヨウ化銅、オキシヨウ化銅等の銅化合物;
イットリウム(III)メトキシド、イットリウム(III)エトキシド、イットリウム(III)プロポキシド、イットリウム(III)イソプロポキシド、イットリウム(III)ブトキシド、イットリウム(III)イソブトキシド、イットリウム(III)ペントキシド、イットリウム(III)アセチルアセトナート、イットリウム(III)イソプロポキシドアセチルアセトナート(Y(acac)(O-iPr)2、Y(acac)2(O-iPr))、トリスジエチルアミノイットリウム、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)イットリウム、イットリウム(III)ヘキサフルオロアセチルアセトナート、トリス-1-メトキシ-2-メチル-2-プロポキシイットリウム(III)、三塩化イットリウム、オキシ塩化イットリウム、三臭化イットリウム、オキシ臭化イットリウム、三ヨウ化イットリウム、オキシヨウ化イットリウム等のイットリウム化合物;
タングステン(VI)メトキシド、タングステン(VI)エトキシド、タングステン(VI)プロポキシド、タングステン(VI)イソプロポキシド、タングステン(VI)ブトキシド、タングステン(VI)イソブトキシド、タングステン(VI)ペントキシド、タングステン(VI)アセチルアセトナート、タングステン(VI)タングステンジイソプロポキシドジアセチルアセトナート(W(acac)3(O-iPr)3)、ヘキサキスジエチルアミノタングステン(VI)、ヘキサキス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)タングステン(VI)、タングステン(VI)ヘキサフルオロアセチルアセトナート、ヘキサキス-1-メトキシ-2-メチル-2-プロポキシタングステン(VI)、六塩化タングステン、四塩化タングステン、オキシ塩化タングステン、六臭化タングステン、四臭化タングステン、オキシ臭化タングステン、六ヨウ化タングステン、四ヨウ化タングステン、オキシヨウ化タングステン等のタングステン化合物;
セリウム(III)メトキシド、セリウム(III)エトキシド、セリウム(III)プロポキシド、セリウム(III)イソプロポキシド、セリウム(III)ブトキシド、セリウム(III)イソブトキシド、セリウム(III)ペントキシド、セリウム(III)アセチルアセトナート、セリウムイソプロポキシドアセチルアセトナート(Ce(acac)(O-iPr)2、Ce(acac)2(O-iPr))、トリスジエチルアミノセリウム、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)セリウム、セリウム(III)ヘキサフルオロアセチルアセトナート、トリス-1-メトキシ-2-メチル-2-プロポキシセリウム(III)、三塩化セリウム、オキシ塩化セリウム、三臭化セリウム、オキシ臭化セリウム、三ヨウ化セリウム、オキシヨウ化セリウム等のセリウム化合物;
アルミニウムメトキシド、アルミニウムエトキシド、アルミニウムプロポキシド、アルミニウムイソプロポキシド、アルミニウムブトキシド、アルミニウムイソブトキシド、アルミニウムペントキシド、アルミニウムアセチルアセトナート、アルミニウムイソプロポキシドアセチルアセトナート(Al(acac)(O-iPr)2、Al(acac)2(O-iPr))、トリスジエチルアミノアルミニウム、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)アルミニウム、アルミニウムヘキサフルオロアセチルアセトナート、トリス-1-メトキシ-2-メチル-2-プロポキシアルミニウム、三塩化アルミニウム、オキシ塩化アルミニウム、三臭化アルミニウム、オキシ臭化アルミニウム、三ヨウ化アルミニウム、オキシヨウ化アルミニウム等のアルミニウム化合物;
ストロンチウムメトキシド、ストロンチウムエトキシド、ストロンチウムプロポキシド、ストロンチウムイソプロポキシド、ストロンチウムブトキシド、ストロンチウムイソブトキシド、ストロンチウムペントキシド、ストロンチウムアセチルアセトナート、ビスジエチルアミノストロンチウム、ビス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)ストロンチウム、ストロンチウムヘキサフルオロアセチルアセトナート、ビス-1-メトキシ-2-メチル-2-プロポキシストロンチウム、二塩化ストロンチウム、オキシ塩化ストロンチウム、二臭化ストロンチウム、オキシ臭化ストロンチウム、二ヨウ化ストロンチウム、オキシヨウ化ストロンチウム等のストロンチウム化合物;
スズ(IV)メトキシド、スズ(IV)エトキシド、スズ(IV)プロポキシド、スズ(IV)イソプロポキシド、スズ(IV)ブトキシド、スズ(IV)イソブトキシド、スズ(IV)ペントキシド、スズ(II)アセチルアセトナート、スズ(IV)ジイソプロポキシドジアセチルアセトナート(Sn(acac)2(O-iPr)2)、テトラキスジエチルアミノスズ、テトラキス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)スズ、スズ(II)ヘキサフルオロアセチルアセトナート、テトラ-1-メトキシ-2-メチル-2-プロポキシスズ(IV)、四塩化スズ、二塩化スズ、オキシ塩化スズ、四臭化スズ、二臭化スズ、オキシ臭化スズ、四ヨウ化スズ、二ヨウ化スズ、オキシヨウ化スズ等のスズ化合物;
が挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。 Specific examples of the metal compound (M1) include
Chromium (III) methoxide, Chromium (III) ethoxide, Chromium (III) propoxide, Chromium (III) isopropoxide, Chromium (III) butoxide, Chromium (III) isobutoxide, Chromium (III) pentoxide, Chromium (III) Acetylacetonate, chromium (III) isopropoxide acetylacetonate (Cr (acac) (O-iPr) 2 , Cr (acac) 2 (O-iPr), acac is acetylacetonate ion, iPr is isopropyl group The same shall apply hereinafter.), Trisdiethylaminochromium, tris (2,2,6,6-tetramethyl-3,5-heptanedione) chromium, chromium (III) hexafluoroacetylacetonate, tri-1- Methoxy-2-methyl-2-propoxychrome (III), chromium trichloride, chromium dichloride, chromium oxychloride, chromium tribromide, chromium dibromide, chromium oxybromide, chromium triiodide, diiodine Chromium, chromium compounds such Okishiyou chromium;
Manganese (III) methoxide, manganese (III) ethoxide, manganese (III) propoxide, manganese (III) isopropoxide, manganese (III) butoxide, manganese (III) isobutoxide, manganese (III) pentoxide, manganese (III) Acetylacetonate, manganese (III) isopropoxide acetylacetonate (Mn (acac) (O-iPr) 2 , Mn (acac) 2 (O-iPr)), trisdiethylaminomanganese, tris (2,2,6, 6-tetramethyl-3,5-heptanedione) manganese, manganese (III) hexafluoroacetylacetonate, tri-1-methoxy-2-methyl-2-propoxymanganese (III), manganese trichloride, manganese dichloride, Manganese such as manganese oxychloride, manganese tribromide, manganese dibromide, manganese oxybromide, manganese triiodide, manganese diiodide, manganese oxyiodide Cancer compounds;
Iron (III) methoxide, iron (III) ethoxide, iron (III) propoxide, iron (III) isopropoxide, iron (III) butoxide, iron (III) isobutoxide, iron (III) pentoxide, iron (III) Acetylacetonate, iron (III) isopropoxide acetylacetonate (Fe (acac) (O-iPr) 2 , Fe (acac) 2 (O-iPr)), trisdiethylaminoiron, tris (2,2,6, 6-tetramethyl-3,5-heptanedione) iron, iron (III) hexafluoroacetylacetonate, tri-1-methoxy-2-methyl-2-propoxyiron (III), iron trichloride, iron dichloride, Iron compounds such as iron oxychloride, iron tribromide, iron dibromide, iron oxybromide, iron triiodide, iron diiodide, iron oxyiodide;
Cobalt (II) methoxide, cobalt (II) ethoxide, cobalt (II) propoxide, cobalt (II) isopropoxide, cobalt (II) butoxide, cobalt (II) isobutoxide, cobalt (II) pentoxide, cobalt (II) Acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) isopropoxide acetylacetonate (Co (acac) (O-iPr)), cobalt (III) isopropoxide acetylacetonate (Co (acac) ( O-iPr) 2 , Co (acac) 2 (O-iPr)), bisdiethylaminocobalt, tris (2,2,6,6-tetramethyl-3,5-heptanedione) cobalt, cobalt (II) hexafluoro Acetylacetonate, tri-1-methoxy-2-methyl-2-propoxycobalt (II), cobalt trichloride, cobalt dichloride, cobalt oxychloride, cobalt tribromide, dibromide Barth, oxy cobalt bromide, triiodide cobalt diiodide, cobalt compounds such as Okishiyou cobalt;
Nickel (II) methoxide, nickel (II) ethoxide, nickel (II) propoxide, nickel (II) isopropoxide, nickel (II) butoxide, nickel (II) isobutoxide, nickel (II) pentoxide, nickel (II) Acetylacetonate, nickel (II) isopropoxide acetylacetonate (Ni (acac) (O-iPr)), bisdiethylaminonickel, bis (2,2,6,6-tetramethyl-3,5-heptanedione) Nickel, nickel (II) hexafluoroacetylacetonate, bis-1-methoxy-2-methyl-2-propoxynickel (II), nickel dichloride, nickel oxychloride, nickel dibromide, nickel oxybromide, diiodo Nickel compounds such as nickel iodide and nickel oxyiodide;
Copper (II) methoxide, copper (II) ethoxide, copper (II) propoxide, copper (II) isopropoxide, copper (II) butoxide, copper (II) isobutoxide, copper (II) pentoxide, copper (II) Acetylacetonate, bisdiethylamino copper, bis (2,2,6,6-tetramethyl-3,5-heptanedione) copper, copper (II) hexafluoroacetylacetonate, bis-1-methoxy-2-methyl- Copper compounds such as 2-propoxy copper (II), copper dichloride, copper oxychloride, copper dibromide, copper oxybromide, copper diiodide, copper oxyiodide;
Yttrium (III) methoxide, yttrium (III) ethoxide, yttrium (III) propoxide, yttrium (III) isopropoxide, yttrium (III) butoxide, yttrium (III) isobutoxide, yttrium (III) pentoxide, yttrium (III) Acetylacetonate, yttrium (III) isopropoxide acetylacetonate (Y (acac) (O-iPr) 2 , Y (acac) 2 (O-iPr)), trisdiethylaminoyttrium, tris (2,2,6, 6-tetramethyl-3,5-heptanedione) yttrium, yttrium (III) hexafluoroacetylacetonate, tris-1-methoxy-2-methyl-2-propoxy yttrium (III), yttrium trichloride, yttrium oxychloride, Yttrium tribromide, yttrium oxybromide, yttrium triiodide, oxy Yttrium compounds such as iodide, yttrium;
Tungsten (VI) methoxide, tungsten (VI) ethoxide, tungsten (VI) propoxide, tungsten (VI) isopropoxide, tungsten (VI) butoxide, tungsten (VI) isobutoxide, tungsten (VI) pentoxide, tungsten (VI) Acetylacetonate, tungsten (VI) tungsten diisopropoxide diacetylacetonate (W (acac) 3 (O-iPr) 3 ), hexakisdiethylaminotungsten (VI), hexakis (2,2,6,6-tetramethyl) -3,5-heptanedione) tungsten (VI), tungsten (VI) hexafluoroacetylacetonate, hexakis-1-methoxy-2-methyl-2-propoxytungsten (VI), tungsten hexachloride, tungsten tetrachloride, oxy Tungsten chloride, tungsten hexabromide, tan tetrabromide Sten, oxybromide tungsten, six iodide tungsten tetraiodide, tungsten, tungsten compounds such Okishiyou tungsten;
Cerium (III) methoxide, cerium (III) ethoxide, cerium (III) propoxide, cerium (III) isopropoxide, cerium (III) butoxide, cerium (III) isobutoxide, cerium (III) pentoxide, cerium (III) Acetylacetonate, cerium isopropoxide acetylacetonate (Ce (acac) (O-iPr) 2 , Ce (acac) 2 (O-iPr)), trisdiethylaminocerium, tris (2,2,6,6-tetra Methyl-3,5-heptanedione) cerium, cerium (III) hexafluoroacetylacetonate, tris-1-methoxy-2-methyl-2-propoxycerium (III), cerium trichloride, cerium oxychloride, tribromide Cerium compounds such as cerium, cerium oxybromide, cerium triiodide, cerium oxyiodide;
Aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum isopropoxide, aluminum butoxide, aluminum isobutoxide, aluminum pentoxide, aluminum acetylacetonate, aluminum isopropoxide acetylacetonate (Al (acac) (O-iPr) 2 , Al (acac) 2 (O-iPr)), trisdiethylaminoaluminum, tris (2,2,6,6-tetramethyl-3,5-heptanedione) aluminum, aluminum hexafluoroacetylacetonate, tris-1 Aluminum compounds such as -methoxy-2-methyl-2-propoxyaluminum, aluminum trichloride, aluminum oxychloride, aluminum tribromide, aluminum oxybromide, aluminum triiodide, aluminum oxyiodide;
Strontium methoxide, strontium ethoxide, strontium propoxide, strontium isopropoxide, strontium butoxide, strontium isobutoxide, strontium pentoxide, strontium acetylacetonate, bisdiethylaminostrontium, bis (2,2,6,6-tetramethyl- 3,5-heptanedione) strontium, strontium hexafluoroacetylacetonate, bis-1-methoxy-2-methyl-2-propoxystrontium, strontium dichloride, strontium oxychloride, strontium dibromide, strontium oxybromide, two Strontium compounds such as strontium iodide and strontium oxyiodide;
Tin (IV) methoxide, tin (IV) ethoxide, tin (IV) propoxide, tin (IV) isopropoxide, tin (IV) butoxide, tin (IV) isobutoxide, tin (IV) pentoxide, tin (II) Acetylacetonate, tin (IV) diisopropoxide diacetylacetonate (Sn (acac) 2 (O-iPr) 2 ), tetrakisdiethylaminotin, tetrakis (2,2,6,6-tetramethyl-3,5- Heptanedione) tin, tin (II) hexafluoroacetylacetonate, tetra-1-methoxy-2-methyl-2-propoxytin (IV), tin tetrachloride, tin dichloride, tin oxychloride, tin tetrabromide, Tin compounds such as tin dibromide, tin oxybromide, tin tetraiodide, tin diiodide, tin oxyiodide;
Is mentioned. These may be used alone or in combination of two or more.
三塩化クロム、二塩化クロム、オキシ塩化クロム、クロム(III)エトキシド、クロム(III)イソプロポキシド、クロム(III)ブトキシド、クロム(III)アセチルアセトナート、クロム(III)イソプロポキシドアセチルアセトナート(Cr(acac)(O-iPr)2、
三塩化マンガン、二塩化マンガン、オキシ塩化マンガン、マンガン(III)エトキシド、マンガン(III)イソプロポキシド、マンガン(III)ブトキシド、マンガン(III)アセチルアセトナート、マンガン(III)イソプロポキシドアセチルアセトナート(Mn(acac)(O-iPr)2、Mn(acac)2(O-iPr)、
三塩化鉄、二塩化鉄、オキシ塩化鉄、鉄(III)エトキシド、鉄(III)イソプロポキシド、鉄(III)ブトキシド、鉄(III)アセチルアセトナート、鉄(III)イソプロポキシドアセチルアセトナート(Fe(acac)(O-iPr)2、Fe(acac)2(O-iPr))、
三塩化コバルト、二塩化コバルト、オキシ塩化コバルト、コバルト(II)エトキシド、コバルト(II)イソプロポキシド、コバルト(II)ブトキシド、コバルト(III)アセチルアセトナート、コバルト(II)イソプロポキシドアセチルアセトナート(Co(acac)(O-iPr))、コバルト(III)イソプロポキシドアセチルアセトナート(Co(acac)(O-iPr)2、Co(acac)2(O-iPr))、
二塩化ニッケル、オキシ塩化ニッケル、ニッケル(II)エトキシド、ニッケル(II)イソプロポキシド、ニッケル(II)ブトキシド、ニッケル(II)アセチルアセトナート、ニッケル(II)イソプロポキシドアセチルアセトナート(Ni(acac)(O-iPr))、
二塩化銅、オキシ塩化銅、銅(II)エトキシド、銅(II)イソプロポキシド、銅(II)ブトキシド、銅(II)アセチルアセトナート、
三塩化イットリウム、オキシ塩化イットリウム、イットリウム(III)エトキシド、イットリウム(III)イソプロポキシド、イットリウム(III)ブトキシド、イットリウム(III)アセチルアセトナート、イットリウム(III)イソプロポキシドアセチルアセトナート(Y(acac)(O-iPr)2、Y(acac)2(O-iPr))、
六塩化タングステン、四塩化タングステン、オキシ塩化タングステン、タングステン(VI)エトキシド、タングステン(VI)イソプロポキシド、タングステン(VI)ブトキシド、タングステン(VI)アセチルアセトナート、タングステン(VI)タングステンジイソプロポキシドジアセチルアセトナート(W(acac)3(O-iPr)3)、
三塩化セリウム、オキシ塩化セリウム、セリウム(III)エトキシド、セリウム(III)イソプロポキシド、セリウム(III)ブトキシド、セリウム(III)アセチルアセトナート、セリウムイソプロポキシドアセチルアセトナート(Ce(acac)(O-iPr)2、Ce(acac)2(O-iPr))、
三塩化アルミニウム、オキシ塩化アルミニウム、アルミニウムエトキシド、アルミニウムイソプロポキシド、アルミニウムブトキシド、アルミニウムアセチルアセトナート、アルミニウムイソプロポキシドアセチルアセトナート(Al(acac)(O-iPr)2、Al(acac)2(O-iPr))、
二塩化ストロンチウム、オキシ塩化ストロンチウム、ストロンチウムエトキシド、ストロンチウムイソプロポキシド、ストロンチウムブトキシド、ストロンチウムアセチルアセトナート、
四塩化スズ、二塩化スズ、オキシ塩化スズ、スズ(IV)メトキシド、スズ(IV)エトキシド、スズ(IV)イソプロポキシド、スズ(IV)ブトキシド、スズ(IV)アセチルアセトナート、スズ(IV)ジイソプロポキシドジアセチルアセトナート(Sn(acac)2(O-iPr)2)が好ましく、
三塩化クロム、二塩化クロム、クロム(III)エトキシド、クロム(III)アセチルアセトナート、
三塩化マンガン、二塩化マンガン、マンガン(III)エトキシド、マンガン(III)アセチルアセトナート、
三塩化鉄、二塩化鉄、鉄(III)エトキシド、鉄(III)イソプロポキシド、鉄(III)ブトキシド、鉄(III)アセチルアセトナート、
三塩化コバルト、二塩化コバルト、コバルト(II)エトキシド、コバルト(II)イソプロポキシド、コバルト(II)ブトキシド、コバルト(III)アセチルアセトナート、
二塩化ニッケル、ニッケル(II)エトキシド、ニッケル(II)イソプロポキシド、ニッケル(II)ブトキシド、ニッケル(II)アセチルアセトナート、
二塩化銅、オキシ塩化銅、銅(II)エトキシド、銅(II)イソプロポキシド、銅(II)アセチルアセトナート、
三塩化イットリウム、イットリウム(III)エトキシド、イットリウム(III)イソプロポキシド、イットリウム(III)アセチルアセトナート、
六塩化タングステン、四塩化タングステン、タングステン(VI)エトキシド、タングステン(VI)イソプロポキシド、タングステン(VI)アセチルアセトナート、
三塩化セリウム、セリウム(III)エトキシド、セリウム(III)イソプロポキシド、セリウム(III)ブトキシド、セリウム(III)アセチルアセトナート、
三塩化アルミニウム、アルミニウムエトキシド、アルミニウムイソプロポキシド、アルミニウムブトキシド、アルミニウムアセチルアセトナート、
二塩化ストロンチウム、ストロンチウムエトキシド、ストロンチウムイソプロポキシド、ストロンチウムブトキシド、ストロンチウムアセチルアセトナート、
四塩化スズ、二塩化スズ、スズ(IV)メトキシド、スズ(IV)エトキシド、スズ(IV)イソプロポキシド、スズ(IV)ブトキシド、スズ(IV)アセチルアセトナートがさらに好ましい。 Among these compounds, the resulting catalyst becomes fine particles with a uniform particle size, and its activity is high,
Chromium trichloride, chromium dichloride, chromium oxychloride, chromium (III) ethoxide, chromium (III) isopropoxide, chromium (III) butoxide, chromium (III) acetylacetonate, chromium (III) isopropoxide acetylacetonate (Cr (acac) (O-iPr) 2 ,
Manganese trichloride, manganese dichloride, manganese oxychloride, manganese (III) ethoxide, manganese (III) isopropoxide, manganese (III) butoxide, manganese (III) acetylacetonate, manganese (III) isopropoxide acetylacetonate (Mn (acac) (O-iPr) 2 , Mn (acac) 2 (O-iPr),
Iron trichloride, iron dichloride, iron oxychloride, iron (III) ethoxide, iron (III) isopropoxide, iron (III) butoxide, iron (III) acetylacetonate, iron (III) isopropoxide acetylacetonate (Fe (acac) (O-iPr) 2 , Fe (acac) 2 (O-iPr)),
Cobalt trichloride, cobalt dichloride, cobalt oxychloride, cobalt (II) ethoxide, cobalt (II) isopropoxide, cobalt (II) butoxide, cobalt (III) acetylacetonate, cobalt (II) isopropoxide acetylacetonate (Co (acac) (O-iPr)), cobalt (III) isopropoxide acetylacetonate (Co (acac) (O-iPr) 2 , Co (acac) 2 (O-iPr)),
Nickel dichloride, nickel oxychloride, nickel (II) ethoxide, nickel (II) isopropoxide, nickel (II) butoxide, nickel (II) acetylacetonate, nickel (II) isopropoxide acetylacetonate (Ni (acac ) (O-iPr)),
Copper dichloride, copper oxychloride, copper (II) ethoxide, copper (II) isopropoxide, copper (II) butoxide, copper (II) acetylacetonate,
Yttrium trichloride, yttrium oxychloride, yttrium (III) ethoxide, yttrium (III) isopropoxide, yttrium (III) butoxide, yttrium (III) acetylacetonate, yttrium (III) isopropoxide acetylacetonate (Y (acac ) (O-iPr) 2 , Y (acac) 2 (O-iPr)),
Tungsten hexachloride, tungsten tetrachloride, tungsten oxychloride, tungsten (VI) ethoxide, tungsten (VI) isopropoxide, tungsten (VI) butoxide, tungsten (VI) acetylacetonate, tungsten (VI) tungsten diisopropoxide diacetyl Acetonate (W (acac) 3 (O-iPr) 3 ),
Cerium trichloride, cerium oxychloride, cerium (III) ethoxide, cerium (III) isopropoxide, cerium (III) butoxide, cerium (III) acetylacetonate, cerium isopropoxide acetylacetonate (Ce (acac) (O -iPr) 2 , Ce (acac) 2 (O-iPr)),
Aluminum trichloride, aluminum oxychloride, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum acetylacetonate, aluminum isopropoxide acetylacetonate (Al (acac) (O-iPr) 2 , Al (acac) 2 ( O-iPr)),
Strontium dichloride, strontium oxychloride, strontium ethoxide, strontium isopropoxide, strontium butoxide, strontium acetylacetonate,
Tin tetrachloride, tin dichloride, tin oxychloride, tin (IV) methoxide, tin (IV) ethoxide, tin (IV) isopropoxide, tin (IV) butoxide, tin (IV) acetylacetonate, tin (IV) Diisopropoxide diacetylacetonate (Sn (acac) 2 (O-iPr) 2 ) is preferred,
Chromium trichloride, chromium dichloride, chromium (III) ethoxide, chromium (III) acetylacetonate,
Manganese trichloride, manganese dichloride, manganese (III) ethoxide, manganese (III) acetylacetonate,
Iron trichloride, iron dichloride, iron (III) ethoxide, iron (III) isopropoxide, iron (III) butoxide, iron (III) acetylacetonate,
Cobalt trichloride, cobalt dichloride, cobalt (II) ethoxide, cobalt (II) isopropoxide, cobalt (II) butoxide, cobalt (III) acetylacetonate,
Nickel dichloride, nickel (II) ethoxide, nickel (II) isopropoxide, nickel (II) butoxide, nickel (II) acetylacetonate,
Copper dichloride, copper oxychloride, copper (II) ethoxide, copper (II) isopropoxide, copper (II) acetylacetonate,
Yttrium trichloride, yttrium (III) ethoxide, yttrium (III) isopropoxide, yttrium (III) acetylacetonate,
Tungsten hexachloride, tungsten tetrachloride, tungsten (VI) ethoxide, tungsten (VI) isopropoxide, tungsten (VI) acetylacetonate,
Cerium trichloride, cerium (III) ethoxide, cerium (III) isopropoxide, cerium (III) butoxide, cerium (III) acetylacetonate,
Aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum acetylacetonate,
Strontium dichloride, strontium ethoxide, strontium isopropoxide, strontium butoxide, strontium acetylacetonate,
Further preferred are tin tetrachloride, tin dichloride, tin (IV) methoxide, tin (IV) ethoxide, tin (IV) isopropoxide, tin (IV) butoxide, and tin (IV) acetylacetonate.
鉄(III)エトキシド、鉄(III)イソプロポキシドアセチルアセトナート(Fe(acac)(O-iPr)2、Fe(acac)2(O-iPr))、鉄(III)アセチルアセトナート、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)鉄(III)、鉄(III)ヘキサフルオロアセチルアセトナート、塩化鉄(II)、塩化鉄(III)、硫酸鉄(III)、硫化鉄(II)、硫化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、フェロシアン化鉄、硝酸鉄(II)、硝酸鉄(III)、シュウ酸鉄(II)、シュウ酸鉄(III)、リン酸鉄(II)、リン酸鉄(III)フェロセン、水酸化鉄(II)、水酸化鉄(III)、酸化鉄(II)、酸化鉄(III)、四酸化三鉄、酢酸鉄(II)、乳酸鉄(II)、クエン酸鉄(III)等の鉄化合物;
ニッケル(II)エトキシド、ニッケル(II)イソプロポキシドアセチルアセトナート(Ni(acac)(O-iPr))、ニッケル(II)アセチルアセトナート、塩化ニッケル(II)、硫酸ニッケル(II)、硫化ニッケル(II)、硝酸ニッケル(II)、シュウ酸ニッケル(II)、リン酸ニッケル(II)、ニッケルセン、水酸化ニッケル(II)、酸化ニッケル(II)、酢酸ニッケル(II)、乳酸ニッケル(II)等のニッケル化合物;
クロム(III)エトキシド、クロム(III)イソプロポキシドアセチルアセトナート(Cr(acac)(O-iPr)2、Cr(acac)2(O-iPr))、クロム(III)アセチルアセトナート、塩化クロム(II)、塩化クロム(III)、硫酸クロム(III)、硫化クロム(III)、硝酸クロム(III)、シュウ酸クロム(III)、リン酸クロム(III)、水酸化クロム(III)、酸化クロム(II)、酸化クロム(III)、酸化クロム(IV)、酸化クロム(VI)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)等のクロム化合物;
コバルト(III)エトキシド、コバルト(III)イソプロポキシドアセチルアセトナート(Co(acac)(O-iPr)2、Co(acac)2(O-iPr))、コバルト(III)アセチルアセトナート、塩化コバルト(II)、塩化コバルト(III)、硫酸コバルト(II)、硫化コバルト(II)、硝酸コバルト(II)、硝酸コバルト(III)、シュウ酸コバルト(II)、リン酸コバルト(II)、コバルトセン、水酸化コバルト(II)、酸化コバルト(II)、酸化コバルト(III)、四酸化三コバルト、酢酸コバルト(II)、乳酸コバルト(II)等のコバルト化合物;
マンガン(III)エトキシド、マンガン(III)イソプロポキシドアセチルアセトナート(Mn(acac)(O-iPr)2、Mn(acac)2(O-iPr))、マンガン(III)アセチルアセトナート、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)マンガン(III)、マンガン(III)ヘキサフルオロアセチルアセトン、塩化マンガン(II)、硫酸マンガン(II)、硫化マンガン(II)、硝酸マンガン(II)、シュウ酸マンガン(II)、水酸化マンガン(II)、酸化マンガン(II)、酸化マンガン(III)、酢酸マンガン(II)、乳酸マンガン(II)、クエン酸マンガン等のマンガン化合物;
が挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。 As a specific example of the transition metal compound (M12),
Iron (III) ethoxide, iron (III) isopropoxide acetylacetonate (Fe (acac) (O-iPr) 2 , Fe (acac) 2 (O-iPr)), iron (III) acetylacetonate, tris ( 2,2,6,6-tetramethyl-3,5-heptanedione) iron (III), iron (III) hexafluoroacetylacetonate, iron (II) chloride, iron (III) chloride, iron (III) sulfate , Iron sulfide (II), iron sulfide (III), potassium ferrocyanide, potassium ferricyanide, ammonium ferrocyanide, ammonium ferricyanide, iron ferrocyanide, iron nitrate (II), iron nitrate (III), iron oxalate ( II), iron (III) oxalate, iron (II) phosphate, iron (III) phosphate ferrocene, iron (II) hydroxide, iron (III) hydroxide, iron (II) oxide, iron (III) oxide , Triiron tetroxide, iron acetate Iron compounds such as (II), iron (II) lactate, iron (III) citrate;
Nickel (II) ethoxide, nickel (II) isopropoxide acetylacetonate (Ni (acac) (O-iPr)), nickel (II) acetylacetonate, nickel (II) chloride, nickel (II) sulfate, nickel sulfide (II), nickel nitrate (II), nickel oxalate (II), nickel phosphate (II), nickel cene, nickel hydroxide (II), nickel oxide (II), nickel acetate (II), nickel lactate (II ) And other nickel compounds;
Chromium (III) ethoxide, Chromium (III) isopropoxide acetylacetonate (Cr (acac) (O-iPr) 2 , Cr (acac) 2 (O-iPr)), Chromium (III) acetylacetonate, Chromium chloride (II), chromium chloride (III), chromium sulfate (III), chromium sulfide (III), chromium nitrate (III), chromium oxalate (III), chromium phosphate (III), chromium hydroxide (III), oxidation Chromium compounds such as chromium (II), chromium oxide (III), chromium oxide (IV), chromium oxide (VI), chromium acetate (II), chromium acetate (III), chromium lactate (III);
Cobalt (III) ethoxide, cobalt (III) isopropoxide acetylacetonate (Co (acac) (O-iPr) 2 , Co (acac) 2 (O-iPr)), cobalt (III) acetylacetonate, cobalt chloride (II), cobalt chloride (III), cobalt sulfate (II), cobalt sulfide (II), cobalt nitrate (II), cobalt nitrate (III), cobalt oxalate (II), cobalt phosphate (II), cobalt cene Cobalt compounds such as cobalt hydroxide (II), cobalt oxide (II), cobalt (III) oxide, tricobalt tetroxide, cobalt (II) acetate and cobalt (II) lactate;
Manganese (III) ethoxide, manganese (III) isopropoxide acetylacetonate (Mn (acac) (O-iPr) 2 , Mn (acac) 2 (O-iPr)), manganese (III) acetylacetonate, tris ( 2,2,6,6-tetramethyl-3,5-heptanedione) manganese (III), manganese (III) hexafluoroacetylacetone, manganese (II) chloride, manganese (II) sulfate, manganese (II) sulfide, nitric acid Manganese compounds such as manganese (II), manganese oxalate (II), manganese hydroxide (II), manganese oxide (II), manganese oxide (III), manganese acetate (II), manganese lactate (II), manganese citrate, etc. ;
Is mentioned. These may be used alone or in combination of two or more.
鉄(III)エトキシド、鉄(III)イソプロポキシドアセチルアセトナート、鉄(III)アセチルアセトナート、塩化鉄(II)、塩化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、酢酸鉄(II)、乳酸鉄(II)、硝酸鉄(II)、
ニッケル(III)エトキシド、ニッケル(III)イソプロポキシドアセチルアセトナート、ニッケル(III)アセチルアセトナート、塩化ニッケル(II)、塩化ニッケル(III)、酢酸ニッケル(II)、乳酸ニッケル(II)、硝酸ニッケル(II)、
クロム(III)エトキシド、クロム(III)イソプロポキシドアセチルアセトナート、クロム(III)アセチルアセトナート、塩化クロム(II)、塩化クロム(III)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)、硝酸クロム(III)、
コバルト(III)エトキシド、コバルト(III)イソプロポキシドアセチルアセトナート、コバルト(III)アセチルアセトナート、塩化コバルト(II)、塩化コバルト(III)、酢酸コバルト(II)、乳酸コバルト(II)、硝酸コバルト(II)、
マンガン(III)エトキシド、マンガン(III)イソプロポキシドアセチルアセトナート、マンガン(III)アセチルアセトナート、塩化マンガン(II)、酢酸マンガン(II)、乳酸マンガン(II)、硝酸マンガン(II)が好ましく、
塩化鉄(II)、塩化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、酢酸鉄(II)、乳酸鉄(II)、塩化クロム(II)、塩化クロム(III)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)がさらに好ましい。 Among these compounds,
Iron (III) ethoxide, iron (III) isopropoxide acetylacetonate, iron (III) acetylacetonate, iron (II) chloride, iron (III) chloride, potassium ferrocyanide, potassium ferricyanide, ammonium ferrocyanide, ferricyan Ammonium chloride, iron (II) acetate, iron (II) lactate, iron (II) nitrate,
Nickel (III) ethoxide, nickel (III) isopropoxide acetylacetonate, nickel (III) acetylacetonate, nickel chloride (II), nickel chloride (III), nickel acetate (II), nickel lactate (II), nitric acid Nickel (II),
Chromium (III) ethoxide, chromium (III) isopropoxide acetylacetonate, chromium (III) acetylacetonate, chromium (II) chloride, chromium (III) chloride, chromium (II) acetate, chromium (III) acetate, lactic acid Chromium (III), chromium (III) nitrate,
Cobalt (III) ethoxide, cobalt (III) isopropoxide acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) chloride, cobalt (III) chloride, cobalt (II) acetate, cobalt (II) lactate, nitric acid Cobalt (II),
Manganese (III) ethoxide, manganese (III) isopropoxide acetylacetonate, manganese (III) acetylacetonate, manganese chloride (II), manganese acetate (II), manganese lactate (II), manganese nitrate (II) are preferred ,
Iron (II) chloride, iron (III) chloride, potassium ferrocyanide, potassium ferricyanide, ammonium ferrocyanide, ammonium ferricyanide, iron (II) acetate, iron (II) lactate, chromium (II) chloride, chromium chloride (III ), Chromium (II) acetate, chromium (III) acetate, and chromium (III) lactate.
チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラプロポキシド、チタンテトライソプロポキシド、チタンテトラブトキシド、チタンテトライソブトキシド、チタンテトラペントキシド、チタンテトラアセチルアセトナート、チタンジイソプロポキシドジアセチルアセトナート(Ti(acac)2(O-iPr)2)チタンオキシジアセチルアセトナート、トリス(アセチルアセトナト)第二チタン塩化物([Ti(acac)3]2[TiCl6])、四塩化チタン、三塩化チタン、オキシ塩化チタン、四臭化チタン、三臭化チタン、オキシ臭化チタン、四ヨウ化チタン、三ヨウ化チタン、オキシヨウ化チタン等のチタン化合物;
ニオブペンタメトキシド、ニオブペンタエトキシド、ニオブペンタイソプロポキシド、ニオブペンタブトキシド、ニオブペンタペントキシド、ニオブトリアセチルアセトナート、ニオブペンタアセチルアセトナート、ニオブジイソプロポキシドトリアセチルアセトナート(Nb(acac)3(O-iPr)2)、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)ニオブ、ニオブ(III)ヘキサフルオロアセチルアセトナート、五塩化ニオブ、オキシ塩化ニオブ、五臭化ニオブ、オキシ臭化ニオブ、五ヨウ化ニオブ、オキシヨウ化ニオブ等のニオブ化合物;
ジルコニウムテトラメトキシド、ジルコニウムテトラエトキシド、ジルコニウムテトラプロポキシド、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキシド、ジルコニウムテトライソブトキシド、ジルコニウムテトラペントキシド、ジルコニウムテトラアセチルアセトナート、ジルコニウムジイソプロポキシドジアセチルアセトナート(Zr(acac)2(O-iPr)2)、テトラキスジエチルアミノジルコニウム、テトラキス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)ジルコニウム、ジルコニウム(IV)ヘキサフルオロアセチルアセトナート、テトラ-1-メトキシ-2-メチル-2-プロポキシジルコニウム(IV)、四塩化ジルコニウム、オキシ塩化ジルコニウム、四臭化ジルコニウム、オキシ臭化ジルコニウム、四ヨウ化ジルコニウム、オキシヨウ化ジルコニウム等のジルコニウム化合物;
タンタルペンタメトキシド、タンタルペンタエトキシド、タンタルペンタイソプロポキシド、タンタルペンタブトキシド、タンタルペンタペントキシド、タンタルテトラエトキシアセチルアセトナート、タンタルジイソプロポキシドジアセチルアセトナート(Ta(acac)2(O-iPr)2)、ペンタキスジエチルアミノタンタル、五塩化タンタル、オキシ塩化タンタル、五臭化タンタル、オキシ臭化タンタル、五ヨウ化タンタル、オキシヨウ化タンタル等のタンタル化合物;
ハフニウムテトラメトキシド、ハフニウムテトラエトキシド、ハフニウムテトラプロポキシド、ハフニウムテトライソプロポキシド、ハフニウムテトラブトキシド、ハフニウムテトライソブトキシド、ハフニウムテトラペントキシド、ハフニウムテトラアセチルアセトナート、テトラキスジエチルアミノハフニウム、テトラ-1-メトキシ-2-メチル-2-プロポキシハフニウム(IV)、ハフニウム(IV)アセチルアセトナート、テトラキス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)ハフニウム、ハフニウム(IV)ヘキサフルオロアセチルアセトン、四塩化ハフニウム、オキシ塩化ハフニウム、臭化ハフニウム、オキシ臭化ハフニウム、ヨウ化ハフニウム、オキシヨウ化ハフニウム等のハフニウム化合物;
バナジウム(V)トリメトキシドオキシド、バナジウム(V)エトキシド、バナジウム(V)トリエトキシドオキシド、バナジウム(V)トリ-i-プロポキシドオキシド、バナジウム(V)トリ-n-ブトキシドオキシド、バナジウム(V)トリ-t-ブトキシドオキシド、バナジウム(V)イソプロポキシドアセチルアセトナート(V(acac)(O-iPr)4、V(acac)2(O-iPr)3、V(acac)3(O-iPr)2、V(acac)4(O-iPr))、バナジウム(III)アセチルアセトナート、バナジウム(III)アセチルアセトン、トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオン)バナジウム(III)、バナジウム(III)ヘキサフルオロアセチルアセトン、塩化バナジウム(II)、塩化バナジウム(III)、塩化バナジウム(IV)、オキシ三塩化バナジウム(V)、臭化バナジウム(III)、オキシ臭化バナジウム(V)、ヨウ化バナジウム(III)、オキシヨウ化バナジウム(V)等のバナジウム化合物;
が挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。 Specific examples of the transition metal compound (M2) include
Titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetraisobutoxide, titanium tetrapentoxide, titanium tetraacetylacetonate, titanium diisopropoxide diacetylacetonate ( Ti (acac) 2 (O-iPr) 2 ) Titanium oxydiacetylacetonate, tris (acetylacetonato) dititanium chloride ([Ti (acac) 3 ] 2 [TiCl 6 ]), titanium tetrachloride, trichloride Titanium compounds such as titanium, titanium oxychloride, titanium tetrabromide, titanium tribromide, titanium oxybromide, titanium tetraiodide, titanium triiodide, titanium oxyiodide;
Niobium pentamethoxide, niobium pentaethoxide, niobium pentaisopropoxide, niobium pentaboxide, niobium pentapentoxide, niobium triacetylacetonate, niobium pentaacetylacetonate, niobium pentaisoacetonate, niobium diisopropoxide triacetylacetonate (Nb (acac 3 ) (O-iPr) 2 ), tris (2,2,6,6-tetramethyl-3,5-heptanedione) niobium, niobium (III) hexafluoroacetylacetonate, niobium pentachloride, niobium oxychloride, Niobium compounds such as niobium pentabromide, niobium oxybromide, niobium pentaiodide, niobium oxyiodide;
Zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraisobutoxide, zirconium tetrapentoxide, zirconium tetraacetylacetonate, zirconium diisopropoxide diacetylacetonate ( Zr (acac) 2 (O-iPr) 2 ), tetrakisdiethylaminozirconium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedione) zirconium, zirconium (IV) hexafluoroacetylacetonate, tetra -1-methoxy-2-methyl-2-propoxyzirconium (IV), zirconium tetrachloride, zirconium oxychloride, zirconium tetrabromide, zirconium oxybromide, zirconium tetraiodide, oxyiodine Zirconium compounds such as zirconium;
Tantalum Pentamethoxide, Tantalum Pentaethoxide, Tantalum Pentaisopropoxide, Tantalum Pentabutoxide, Tantalum Pentapentoxide, Tantalum Tetraethoxyacetylacetonate, Tantalum Diisopropoxide Diacetylacetonate (Ta (acac) 2 (O-iPr 2 ), tantalum compounds such as pentakisdiethylaminotantalum, tantalum pentachloride, tantalum oxychloride, tantalum pentabromide, tantalum oxybromide, tantalum pentaiodide, tantalum oxyiodide;
Hafnium tetramethoxide, hafnium tetraethoxide, hafnium tetrapropoxide, hafnium tetraisopropoxide, hafnium tetrabutoxide, hafnium tetraisobutoxide, hafnium tetrapentoxide, hafnium tetraacetylacetonate, tetrakisdiethylaminohafnium, tetra-1-methoxy -2-Methyl-2-propoxyhafnium (IV), hafnium (IV) acetylacetonate, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedione) hafnium, hafnium (IV) hexafluoroacetylacetone Hafnium compounds such as hafnium tetrachloride, hafnium oxychloride, hafnium bromide, hafnium oxybromide, hafnium iodide, hafnium oxyiodide;
Vanadium (V) trimethoxide oxide, vanadium (V) ethoxide, vanadium (V) triethoxide oxide, vanadium (V) tri-i-propoxide oxide, vanadium (V) tri-n-butoxide oxide, vanadium (V ) Tri-t-butoxide oxide, vanadium (V) isopropoxide acetylacetonate (V (acac) (O-iPr) 4 , V (acac) 2 (O-iPr) 3 , V (acac) 3 (O- iPr) 2 , V (acac) 4 (O-iPr)), vanadium (III) acetylacetonate, vanadium (III) acetylacetone, tris (2,2,6,6-tetramethyl-3,5-heptanedione) Vanadium (III), vanadium (III) hexafluoroacetylacetone, vanadium (II) chloride, vanadium (III) chloride, vanadium (IV) chloride, vanadium oxytrichloride (V), odor Vanadium (III), oxybromide vanadium (V), iodide vanadium (III), vanadium compounds such Okishiyou vanadium (V);
Is mentioned. These may be used alone or in combination of two or more.
チタンテトラエトキシド、四塩化チタン、オキシ塩化チタン、チタンテトライソプロポキシド、チタンテトラアセチルアセトナート、チタンジイソプロポキシドジアセチルアセトナート(Ti(acac)2(O-iPr)2)、
ニオブペンタエトキシド、五塩化ニオブ、オキシ塩化ニオブ、ニオブペンタイソプロポキシド、ニオブペンタアセチルアセトナート、ニオブトリアセチルアセトナート、ニオブジイソプロポキシドトリアセチルアセトナート(Nb(acac)3(O-iPr)2)、
ジルコニウムテトラエトキシド、四塩化ジルコニウム、オキシ塩化ジルコニウム、ジルコニウムテトライソプロポキシド、ジルコニウムテトラアセチルアセトナート、ジルコニウムジイソプロポキシドジアセチルアセトナート(Zr(acac)2(O-iPr)2)、
タンタルペンタメトキシド、タンタルペンタエトキシド、五塩化タンタル、オキシ塩化タンタル、タンタルペンタイソプロポキシド、タンタルテトラエトキシアセチルアセトナート(Ta(acac)(O-C2H5)4)、タンタルジイソプロポキシドトリアセチルアセトナート(Ta(acac)3(O-iPr)2)、
バナジウム(V)トリメトキシドオキシド、バナジウム(V)エトキシド、バナジウム(V)トリエトキシドオキシド、バナジウム(V)トリ-i-プロポキシドオキシド、バナジウム(V)トリ-n-ブトキシドオキシド、バナジウム(V)トリ-t-ブトキシドオキシド、バナジウム(V)イソプロポキシドアセチルアセトナート(V(acac)(O-iPr)4、V(acac)2(O-iPr)3、V(acac)3(O-iPr)2、V(acac)4(O-iPr))、バナジウム(III)アセチルアセトナート、バナジウム(III)アセチルアセトン、塩化バナジウム(III)、塩化バナジウム(IV)が好ましく、
五塩化チタン、チタンテトライソプロポキシド、チタンテトラアセチルアセトナート、ニオブペンタエトキシド、ニオブペンタイソプロポキシド、四塩化ジルコニウム、オキシ塩化ジルコニウム、ジルコニウムテトライソプロポキシド、タンタルペンタイソプロポキシド、バナジウム(V)トリ-i-プロポキシドオキシド、バナジウム(III)アセチルアセトン、塩化バナジウム(III)がさらに好ましい。 Among these compounds, the resulting catalyst becomes fine particles with a uniform particle size, and its activity is high,
Titanium tetraethoxide, titanium tetrachloride, titanium oxychloride, titanium tetraisopropoxide, titanium tetraacetylacetonate, titanium diisopropoxide diacetylacetonate (Ti (acac) 2 (O-iPr) 2 ),
Niobium pentaethoxide, niobium pentachloride, niobium oxychloride, niobium pentaisopropoxide, niobium pentaacetylacetonate, niobium triacetylacetonate, niobium diisopropoxide triacetylacetonate (Nb (acac) 3 (O-iPr 2 ),
Zirconium tetraethoxide, zirconium tetrachloride, zirconium oxychloride, zirconium tetraisopropoxide, zirconium tetraacetylacetonate, zirconium diisopropoxide diacetylacetonate (Zr (acac) 2 (O-iPr) 2 ),
Tantalum pentamethoxide, tantalum pentaethoxide, tantalum pentachloride, tantalum oxychloride, tantalum pentaisopropoxide, tantalum tetraethoxyacetylacetonate (Ta (acac) (OC 2 H 5 ) 4 ), tantalum diisopropoxide tri Acetylacetonate (Ta (acac) 3 (O-iPr) 2 ),
Vanadium (V) trimethoxide oxide, vanadium (V) ethoxide, vanadium (V) triethoxide oxide, vanadium (V) tri-i-propoxide oxide, vanadium (V) tri-n-butoxide oxide, vanadium (V ) Tri-t-butoxide oxide, vanadium (V) isopropoxide acetylacetonate (V (acac) (O-iPr) 4 , V (acac) 2 (O-iPr) 3 , V (acac) 3 (O- iPr) 2 , V (acac) 4 (O-iPr)), vanadium (III) acetylacetonate, vanadium (III) acetylacetone, vanadium chloride (III), vanadium chloride (IV) are preferred,
Titanium pentachloride, titanium tetraisopropoxide, titanium tetraacetylacetonate, niobium pentaethoxide, niobium pentaisopropoxide, zirconium tetrachloride, zirconium oxychloride, zirconium tetraisopropoxide, tantalum pentaisopropoxide, vanadium (V More preferred are tri-i-propoxide oxide, vanadium (III) acetylacetone and vanadium (III) chloride.
前記窒素含有有機化合物(2)としては、前記金属化合物(1)中の金属原子に配位可能な配位子となり得る化合物(好ましくは、単核の錯体を形成し得る化合物)が好ましく、多座配位子(好ましくは、2座配位子または3座配位子)となり得る(キレートを形成し得る)化合物がさらに好ましい。 <Nitrogen-containing organic compound (2)>
The nitrogen-containing organic compound (2) is preferably a compound that can be a ligand capable of coordinating to the metal atom in the metal compound (1) (preferably a compound that can form a mononuclear complex). More preferred are compounds that can be bidentate (preferably bidentate or tridentate) (can form chelates).
本発明の製造方法においては、工程(1)において、さらに以下の化合物(3)も混合することによって、さらに高い触媒活性を有する電極触媒が製造することができる。 <Compound (3)>
In the production method of the present invention, an electrode catalyst having higher catalytic activity can be produced by further mixing the following compound (3) in step (1).
テトラフルオロホウ酸四級アンモニウム塩(たとえば、テトラフルオロホウ酸テトラ-n-ブチルアンモニウム、テトラフルオロホウ酸テトラメチルアンモニウム、テトラフルオロホウ酸テトラエチルアンモニウム、テトラフルオロホウ酸テトラプロピルアンモニウム、テトラフルオロホウ酸テトラブチルアンモニウム、テトラフルオロホウ酸エチルトリメチルアンモニウム、テトラフルオロホウ酸ジエチルジメチルアンモニウム、テトラフルオロホウ酸トリエチルメチルアンモニウム、テトラフルオロホウ酸メチルトリプロピルアンモニウム、テトラフルオロホウ酸エチルトリプロピルアンモニウム、テトラフルオロホウ酸トリメチルプロピルアンモニウム、テトラフルオロホウ酸エチルジメチルプロピルアンモニウム、テトラフルオロホウ酸ジエチルメチルプロピルアンモニウム、テトラフルオロホウ酸トリエチルプロピルアンモニウム、テトラフルオロホウ酸ジメチルジプロピルアンモニウム、テトラフルオロホウ酸エチルメチルジプロピルアンモニウム、テトラフルオロホウ酸ジエチルジプロピルアンモニウム、テトラフルオロホウ酸トリメチルブチルアンモニウム、テトラフルオロホウ酸エチルジメチルブチルアンモニウム、テトラフルオロホウ酸ジエチルメチルブチルアンモニウム、テトラフルオロホウ酸トリエチルブチルアンモニウム、テトラフルオロホウ酸トリプロピルブチルアンモニウム、テトラフルオロホウ酸ジメチルジブチルアンモニウム、テトラフルオロホウ酸エチルメチルジブチルアンモニウム、テトラフルオロホウ酸ジエチルジブチルアンモニウム、テトラフルオロホウ酸へキシルトリメチルアンモニウム(前記プロピルはn-プロピル、i-プロピルを含み、前記ブチルはn-ブチル、i-ブチル、s-ブチル、t-ブチルを含む。))、
テトラフルオロホウ酸四級ピリジニウム塩(たとえば、テトラフルオロホウ酸ピリジニウム、テトラフルオロホウ酸1-メチルピリジニウム、テトラフルオロホウ酸2-ブロモ-1-エチルピリジニウム、テトラフルオロホウ酸1-ブチルピリジニウム)、
テトラフルオロホウ酸四級イミダゾリウム塩(たとえば、テトラフルオロホウ酸1,3-ジメチルイミダゾリウム、テトラフルオロホウ酸1-エチル-3-メチルイミダゾリウム、テトラフルオロホウ酸1,3-ジエチルイミダゾリウム、テトラフルオロホウ酸1,2-ジメチル-3-エチルイミダゾリウム、テトラフルオロホウ酸1,2-ジメチル-3-プロピルイミダゾリウム、テトラフルオロホウ酸1-ブチル-3-メチルイミダゾリウム)、
アルキル基の水素原子の全部または一部がフッ素原子で置換されたフルオロアルキルホウ酸(たとえば、ノナコサデカフルオロテトラデシルホウ酸、ヘプタコサデカフルオロトリデシルホウ酸、ペンタコサデカフルオロドデシルホウ酸、トリコサデカフルオロウンデシルホウ酸、ヘンイコサデカフルオロデシルホウ酸、ノナデカフルオロノニルホウ酸、ヘプタデカフルオロオクチルホウ酸、ペンタデカフルオロヘプチルホウ酸、トリデカフルオロヘキシルホウ酸、ウンデカフルオロペンチルホウ酸、ノナフルオロブチルホウ酸、ヘプタフルオロプロピルホウ酸、ペンタフルオロエチルホウ酸、トリフルオロメチルホウ酸および2,2,2-トリフルオロエチルホウ酸)
前記フルオロアルキルホウ酸のモノエステルおよびジエステル(たとえば、メチルエステル、エチルエステル)、および
前記フルオロアルキルホウ酸の塩(たとえば、ナトリウム塩、カリウム塩、アンモニウム塩、メチルアンモニウム塩、ジメチルアンモニウム塩、トリメチルアンモニウム塩、およびトリエチルアンモニウム塩)、
が挙げられる。 As the boric acid derivative containing fluorine, for example,
Tetrafluoroboric acid quaternary ammonium salts (eg, tetra-n-butylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrafluoroborate tetra Butyl ammonium, ethyl trimethyl ammonium tetrafluoroborate, diethyl dimethyl ammonium tetrafluoroborate, triethyl methyl ammonium tetrafluoroborate, methyl tripropyl ammonium tetrafluoroborate, ethyl tripropyl ammonium tetrafluoroborate, trimethyl tetrafluoroborate Propyl ammonium, ethyl dimethylpropyl ammonium tetrafluoroborate, tetrafluorophospho Diethylmethylpropylammonium acid, triethylpropylammonium tetrafluoroborate, dimethyldipropylammonium tetrafluoroborate, ethylmethyldipropylammonium tetrafluoroborate, diethyldipropylammonium tetrafluoroborate, trimethylbutylammonium tetrafluoroborate, Ethyldimethylbutylammonium tetrafluoroborate, diethylmethylbutylammonium tetrafluoroborate, triethylbutylammonium tetrafluoroborate, tripropylbutylammonium tetrafluoroborate, dimethyldibutylammonium tetrafluoroborate, ethylmethyldibutyltetrafluoroborate Ammonium, diethyldibutylammonium tetrafluoroborate, Hexyl trimethylammonium the tiger tetrafluoroborate (the propyl includes n- propyl, i- propyl, the butyl is n- butyl, i- butyl, s- butyl, including t- butyl.)),
Quaternary pyridinium tetrafluoroborate (eg, pyridinium tetrafluoroborate, 1-methylpyridinium tetrafluoroborate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 1-butylpyridinium tetrafluoroborate),
Tetrafluoroborate quaternary imidazolium salts (for example, 1,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,3-diethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-ethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate),
Fluoroalkylboric acid in which all or part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (for example, nonacosadecafluorotetradecylboric acid, heptacosadecafluorotridecylboric acid, pentacosadecafluorododecylboric acid, Tricosa decafluoroundecyl boric acid, Henicosa decafluorodecyl boric acid, Nonadecafluorononyl boric acid, Heptadecafluorooctyl boric acid, Pentadecafluoroheptyl boric acid, Tridecafluorohexyl boric acid, Undecafluoropentyl Boric acid, nonafluorobutyl boric acid, heptafluoropropyl boric acid, pentafluoroethyl boric acid, trifluoromethyl boric acid and 2,2,2-trifluoroethyl boric acid)
Monoesters and diesters of the fluoroalkylboric acid (for example, methyl ester, ethyl ester), and salts of the fluoroalkylboric acid (for example, sodium salt, potassium salt, ammonium salt, methylammonium salt, dimethylammonium salt, trimethylammonium salt) Salt, and triethylammonium salt),
Is mentioned.
ヘキサフルオロリン酸塩、たとえば、ヘキサフルオロリン酸四級アンモニウム塩(たとえば、ヘキサフルオロリン酸テトラ‐n‐ブチルアンモニウム、ヘキサフルオロリン酸テトラメチルアンモニウム、ヘキサフルオロリン酸テトラエチルアンモニウム、ヘキサフルオロリン酸テトラプロピルアンモニウム、ヘキサフルオロリン酸テトラブチルアンモニウム、ヘキサフルオロリン酸エチルトリメチルアンモニウム、ヘキサフルオロリン酸ジエチルジメチルアンモニウム、ヘキサフルオロリン酸トリエチルメチルアンモニウム、ヘキサフルオロリン酸メチルトリプロピルアンモニウム、ヘキサフルオロリン酸エチルトリプロピルアンモニウム、ヘキサフルオロリン酸トリメチルプロピルアンモニウム、ヘキサフルオロリン酸エチルジメチルプロピルアンモニウム、ヘキサフルオロリン酸ジエチルメチルプロピルアンモニウム、ヘキサフルオロリン酸トリエチルプロピルアンモニウム、ヘキサフルオロリン酸ジメチルジプロピルアンモニウム、ヘキサフルオロリン酸エチルメチルジプロピルアンモニウム、ヘキサフルオロリン酸ジエチルジプロピルアンモニウム、ヘキサフルオロリン酸トリメチルブチルアンモニウム、ヘキサフルオロリン酸エチルジメチルブチルアンモニウム、ヘキサフルオロリン酸ジエチルメチルブチルアンモニウム、ヘキサフルオロリン酸トリエチルブチルアンモニウム、ヘキサフルオロリン酸トリプロピルブチルアンモニウム、ヘキサフルオロリン酸ジメチルジブチルアンモニウム、ヘキサフルオロリン酸エチルメチルジブチルアンモニウム、ヘキサフルオロリン酸ジエチルジブチルアンモニウム、テトラフルオロリン酸へキシルトリメチルアンモニウム(前記プロピルはn-プロピル、i-プロピル、前記ブチルはn-ブチル、i-ブチル、s-ブチル、t-ブチルを含む。)、
ヘキサフルオロリン酸四級ピリジニウム塩(たとえば、ヘキサフルオロリン酸ピリジニウム、ヘキサフルオロリン酸1-メチルピリジニウム、ヘキサフルオロリン酸2-ブロモ-1-エチルピリジニウム)、
テトラフルオロリン酸四級イミダゾリウム塩(たとえば、テトラフルオロリン酸1,3-ジメチルイミダゾリウム、テトラフルオロリン酸1-エチル-3-メチルイミダゾリウム、テトラフルオロリン酸1,3-ジエチルイミダゾリウム、テトラフルオロリン酸1,2-ジメチル-3-エチルイミダゾリウム、テトラフルオロリン酸1,2-ジメチル-3-プロピルイミダゾリウム、テトラフルオロリン酸1-ブチル-3-メチルイミダゾリウム)、
ヘキサフルオロリン酸、
前記ヘキサフルオロリン酸の塩(たとえば、ナトリウム塩、カリウム塩、アンモニウム塩、アルキルアンモニウム(たとえば、メチルアンモニウム、ジメチルアンモニウム、トリメチルアンモニウム、エチルアンモニウム、ジエチルアンモニウム、およびトリエチルアンモニウム)塩)
一般式:(RO)nP=Oで表わされるフルオロアルキルリン酸エステル(式中、nは1~3であり、Rはアルキル基の水素原子の全部または一部がフッ素原子で置換されたフルオロアルキル基(たとえば、ノナコサデカフルオロテトラデシル基、ノナコサデカフルオロテトラデシル基、ヘプタコサデカフルオロトリデシル基、ペンタコサデカフルオロドデシル基、トリコサデカフルオロウンデシル基、ヘンイコサデカフルオロデシル基、ノナデカフルオロノニル基、ヘプタデカフルオロオクチル基、ペンタデカフルオロヘプチル基、トリデカフルオロヘキシル基、ウンデカフルオロペンチル基、ノナフルオロブチル基、ヘプタフルオロプロピル基、ペンタフルオロエチル基、トリフルオロメチル基および2,2,2-トリフルオロエチル基)である。)、
一般式:(RN)3P=O、(RN)2P=O(OH)、または(RN)P=O(OH)2(式中、Rは前記フルオロアルキル基を表す。)で表されるフルオロアルキルリン酸アミド、
一般式(RO)3P、(RO)2(OH)P、または(RO)(OH)2P(式中、前記フルオロアルキル基を表す。)で表わされるフルオロアルキル亜リン酸、
一般式(RN)3P、(RN)2P(OH)、(RN)P(OH)2(式中、Rは前記フルオロアルキル基を表す。)で表わされるフルオロアルキル亜リン酸アミド、
一般式:RPO(OH)2(式中、Rは前記フルオロアルキル基を表す。)で表わされるフルオロアルキルホスホン酸。
が挙げられる。 As the phosphoric acid derivative containing fluorine,
Hexafluorophosphates such as hexafluorophosphate quaternary ammonium salts (eg tetra-n-butylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrahexafluorophosphate) Propylammonium, tetrabutylammonium hexafluorophosphate, ethyltrimethylammonium hexafluorophosphate, diethyldimethylammonium hexafluorophosphate, triethylmethylammonium hexafluorophosphate, methyltripropylammonium hexafluorophosphate, ethyltrifluorohexaphosphate Propylammonium, trimethylpropylammonium hexafluorophosphate, ethyldimethyl hexafluorophosphate Ruammonium, diethylmethylpropylammonium hexafluorophosphate, triethylpropylammonium hexafluorophosphate, dimethyldipropylammonium hexafluorophosphate, ethylmethyldipropylammonium hexafluorophosphate, diethyldipropylammonium hexafluorophosphate, hexafluoro Trimethylbutylammonium phosphate, ethyldimethylbutylammonium hexafluorophosphate, diethylmethylbutylammonium hexafluorophosphate, triethylbutylammonium hexafluorophosphate, tripropylbutylammonium hexafluorophosphate, dimethyldibutylammonium hexafluorophosphate, hexa Ethyl methyl dibutyl ammonium fluorophosphate, hexafluoro Diethyl dibutyl ammonium, hexyl trimethylammonium the tetrafluoro phosphate (including the propyl n- propyl, i- propyl, the butyl is n- butyl, i- butyl, s- butyl, t- butyl.),
Quaternary pyridinium hexafluorophosphate (eg, pyridinium hexafluorophosphate, 1-methylpyridinium hexafluorophosphate, 2-bromo-1-ethylpyridinium hexafluorophosphate),
Tetrafluorophosphate quaternary imidazolium salts (for example, 1,3-dimethylimidazolium tetrafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluorophosphate, 1,3-diethylimidazolium tetrafluorophosphate, 1,2-dimethyl-3-ethylimidazolium tetrafluorophosphate, 1,2-dimethyl-3-propylimidazolium tetrafluorophosphate, 1-butyl-3-methylimidazolium tetrafluorophosphate),
Hexafluorophosphoric acid,
Salts of the hexafluorophosphoric acid (for example, sodium salt, potassium salt, ammonium salt, alkylammonium (for example, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, and triethylammonium) salts)
Fluoroalkyl phosphate represented by the general formula: (RO) n P = O (wherein n is 1 to 3 and R is a fluoro having all or part of the hydrogen atoms of the alkyl group substituted with fluorine atoms) Alkyl groups (for example, nonacosadecafluorotetradecyl group, nonacosadecafluorotetradecyl group, heptacosadecafluorotridecyl group, pentacosadecafluorododecyl group, tricosadecafluoroundecyl group, henicosadecafluorodecyl group) Group, nonadecafluorononyl group, heptadecafluorooctyl group, pentadecafluoroheptyl group, tridecafluorohexyl group, undecafluoropentyl group, nonafluorobutyl group, heptafluoropropyl group, pentafluoroethyl group, trifluoromethyl Group and 2,2,2-trifluoroethyl group) .),
General formula: (RN) 3 P═O, (RN) 2 P═O (OH), or (RN) P═O (OH) 2 (wherein R represents the fluoroalkyl group). Fluoroalkyl phosphoric acid amide,
A fluoroalkylphosphorous acid represented by the general formula (RO) 3 P, (RO) 2 (OH) P, or (RO) (OH) 2 P (wherein the above-mentioned fluoroalkyl group is represented),
A fluoroalkyl phosphite amide represented by the general formula (RN) 3 P, (RN) 2 P (OH), (RN) P (OH) 2 (wherein R represents the fluoroalkyl group),
A fluoroalkylphosphonic acid represented by the general formula: RPO (OH) 2 (wherein R represents the fluoroalkyl group).
Is mentioned.
テトラフルオロエチレンとパーフルオロ[2-(フルオロスルホニルエトキシ)プロピルビニルエーテル]との共重合体(たとえば、ナフィオン(NAFION(登録商標)、下式で表わされる構造を有する共重合体))、 As the sulfonic acid derivative containing fluorine,
A copolymer of tetrafluoroethylene and perfluoro [2- (fluorosulfonylethoxy) propyl vinyl ether] (for example, NAFION (registered trademark), a copolymer having a structure represented by the following formula)),
前記フルオロアルキルスルホン酸のエステル(たとえば、メチルエステル、エチルエステル、アリールエステル(例えば、フェニルエステル))
前記フルオロアルキルスルホン酸の塩(一般式:A[RSO3]、Rは前記フルオロアルキル基を表す。)(ナトリウム塩、カリウム塩、アンモニウム塩、アルキルアンモニウム(たとえば、メチルアンモニウム、ジメチルアンモニウム、トリメチルアンモニウム、エチルアンモニウム、ジエチルアンモニウム、およびトリエチルアンモニウム)塩)、
前記フルオロアルキルスルホン酸のアミド(一般式:R-SO2-NR1R2、Rは前記フルオロアルキル基を、R1およびR2はそれぞれ独立に、水素原子の全部または一部がフッ素原子で置換されていてもよい炭素原子数1~10の炭化水素基(たとえば、メチル基、エチル基、フェニル基)表す。)、
前記フルオロアルキルスルホン酸の酸無水物(一般式:(R-SO2)2O、Rは前記フルオロアルキル基を表す。)、
前記フルオロアルキルスルホン酸のハロゲン化物(一般式:(R-SO2)X、Rは前記フルオロアルキル基を表す。Xはフッ素、塩素、臭素、ヨウ素を表す。)
が挙げられる。 Fluoroalkylsulfonic acid in which all or part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (the number of carbon atoms is, for example, 1 to 30) (for example, nonacosadecafluorotetradecanesulfonic acid, heptacosadecafluoro Tridecanesulfonic acid, pentacosadecafluorododecanesulfonic acid, tricosadecafluoroundecanesulfonic acid, henicosadecafluorodecanesulfonic acid, nonadecafluorononanesulfonic acid, heptadecafluorooctanesulfonic acid, pentadecafluoroheptanesulfonic acid , Tridecafluorohexanesulfonic acid, undecafluoropentanesulfonic acid, nonafluorobutanesulfonic acid, heptafluoropropanesulfonic acid, pentafluoroethanesulfonic acid, trifluoromethanesulfonic acid and 2,2, 2-trifluoroethanesulfonic acid),
Esters of the fluoroalkylsulfonic acid (for example, methyl ester, ethyl ester, aryl ester (for example, phenyl ester))
Salt of fluoroalkylsulfonic acid (general formula: A [RSO 3 ], R represents the fluoroalkyl group) (sodium salt, potassium salt, ammonium salt, alkylammonium (eg, methylammonium, dimethylammonium, trimethylammonium) , Ethylammonium, diethylammonium, and triethylammonium) salts),
Amide of the fluoroalkylsulfonic acid (general formula: R—SO 2 —NR 1 R 2 , R is the fluoroalkyl group, R 1 and R 2 are each independently, all or part of the hydrogen atoms are fluorine atoms An optionally substituted hydrocarbon group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, or a phenyl group);
Acid anhydride of the fluoroalkylsulfonic acid (general formula: (R—SO 2 ) 2 O, R represents the fluoroalkyl group),
Halogenated fluoroalkylsulfonic acid (general formula: (R—SO 2 ) X, R represents the fluoroalkyl group. X represents fluorine, chlorine, bromine, iodine.)
Is mentioned.
より好ましくは、トリフルオロメタンスルホン酸、ヘプタデカフルオロオクタンスルホン酸、ノナフルオロ-1-ブタンスルホン酸、トリフルオロメタンスルホン酸テトラブチルアンモニウム、ヘプタデカフルオロオクタンスルホン酸アンモニウム、トリフルオロメタンスルホン酸第一鉄が挙げられ、
さらに、界面活性能がある骨格つまり、分子内に疎水性部位と親水性部位が存在すると反応系内の安定化がはかれるのでさらに好ましい。 The fluorine-containing sulfonic acid derivative is preferably a copolymer of tetrafluoroethylene and perfluoro [2- (fluorosulfonylethoxy) propyl vinyl ether] (for example, NAFION (registered trademark)), heptadeca Fluorooctanesulfonic acid, pentadecafluoroheptanesulfonic acid, tridecafluorohexanesulfonic acid, undecafluoropentanesulfonic acid, nonafluorobutanesulfonic acid, heptafluoropropanesulfonic acid, pentafluoroethanesulfonic acid, trifluoromethanesulfonic acid, hepta Ammonium decafluorooctane sulfonate, ammonium pentadecafluoroheptane sulfonate, ammonium tridecafluorohexane sulfonate, undecafluoropentance Ammonium phonate, ammonium nonafluorobutanesulfonate, ammonium heptafluoropropanesulfonate, ammonium pentafluoroethanesulfonate, ammonium trifluoromethanesulfonate, trimethylammonium trifluoromethanesulfonate, triethylammonium trifluoromethanesulfonate, tributyl trifluoromethanesulfonate Ammonium, tetramethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoromethanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, nonafluoro-1-butanesulfonic acid, trifluoromethanesulfonic acid Ferrous iron, trifle B methanesulfonic anhydride and the like,
More preferably, trifluoromethanesulfonic acid, heptadecafluorooctanesulfonic acid, nonafluoro-1-butanesulfonic acid, tetrabutylammonium trifluoromethanesulfonate, ammonium heptadecafluorooctanesulfonate, and ferrous trifluoromethanesulfonate can be mentioned. ,
Furthermore, it is more preferable that a skeleton having a surface active ability, that is, a hydrophobic site and a hydrophilic site in the molecule can stabilize the reaction system.
前記溶媒としては、たとえば水、アルコール類および酸類が挙げられる。アルコール類としては、エタノール、メタノール、ブタノール、プロパノールおよびエトキシエタノールが好ましく、エタノールおよびメタノールがさらに好ましい。酸類としては、酢酸、硝酸(水溶液)、塩酸、リン酸水溶液およびクエン酸水溶液が好ましく、酢酸および硝酸がさらに好ましい。これらは、1種単独で用いてもよく2種以上を併用してもよい。 <Solvent>
Examples of the solvent include water, alcohols and acids. As alcohols, ethanol, methanol, butanol, propanol and ethoxyethanol are preferable, and ethanol and methanol are more preferable. As the acids, acetic acid, nitric acid (aqueous solution), hydrochloric acid, phosphoric acid aqueous solution and citric acid aqueous solution are preferable, and acetic acid and nitric acid are more preferable. These may be used alone or in combination of two or more.
前記金属化合物(1)が、ハロゲン原子を含む場合には、これらの化合物は一般的に水によって容易に加水分解され、水酸化物や、酸塩化物等の沈殿を生じやすい。よって、前記金属化合物(1)がハロゲン原子を含む場合には、強酸を溶液(触媒前駆体溶液)中に1重量%以上となる量で添加することが好ましい。たとえば酸が塩酸であれば、溶液(触媒前駆体溶液)中の塩化水素の濃度が5重量%以上、より好ましくは10重量%以上となるように酸を添加すると、前記金属化合物(1)に由来する水酸化物、酸塩化物等の沈殿の発生を抑制しつつ、澄明な触媒前駆体溶液を得ることができる。 <Precipitation inhibitor>
When the metal compound (1) contains a halogen atom, these compounds are generally easily hydrolyzed by water, and precipitates such as hydroxides and acid chlorides are easily generated. Therefore, when the metal compound (1) contains a halogen atom, it is preferable to add a strong acid in the solution (catalyst precursor solution) in an amount of 1% by weight or more. For example, when the acid is hydrochloric acid, the acid is added to the metal compound (1) by adding an acid such that the concentration of hydrogen chloride in the solution (catalyst precursor solution) is 5 wt% or more, more preferably 10 wt% or more. A clear catalyst precursor solution can be obtained while suppressing the occurrence of precipitation of the derived hydroxide, acid chloride and the like.
工程(2)では、工程(1)で得られた前記触媒前駆体溶液から溶媒を除去する。 (Process (2))
In step (2), the solvent is removed from the catalyst precursor solution obtained in step (1).
工程(3)では、工程(2)で得られた固形分残渣を熱処理して電極触媒を得る。 (Process (3))
In the step (3), the solid residue obtained in the step (2) is heat-treated to obtain an electrode catalyst.
本発明の熱処理物は、
少なくとも金属化合物(1)と、窒素含有有機化合物(2)と、溶媒と、任意にホウ素、リンおよび硫黄からなる群から選ばれる少なくとも1種の元素Aならびにフッ素を含有する化合物(3)とを混合して触媒前駆体溶液を得る工程(1)、
前記触媒前駆体溶液から溶媒を除去する工程(2)、および
工程(2)で得られた固形分残渣を500~1100℃の温度で熱処理する工程(3)
を経て得られ、
前記金属化合物(1)の一部または全部が、金属元素として周期表第4族および第5族の元素から選ばれる少なくとも1種の金属元素M1を含有する金属化合物(M1)であり、
前記工程(1)で用いられる成分のうち溶媒以外の少なくとも1つの成分が酸素原子を有する(すなわち、前記化合物(3)を用いる場合には、化合物(1)、化合物(2)および化合物(3)の少なくとも1つが酸素原子を有し、化合物(3)を用いない場合には、化合物(1)および化合物(2)の少なくとも1つが酸素原子を有する)
ことを特徴としている。 [Heat-treated product]
The heat-treated product of the present invention is
At least a metal compound (1), a nitrogen-containing organic compound (2), a solvent, and optionally a compound (3) containing at least one element A selected from the group consisting of boron, phosphorus and sulfur and fluorine. Mixing to obtain a catalyst precursor solution (1),
Step (2) for removing the solvent from the catalyst precursor solution, and Step (3) for heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
Obtained through
A part or all of the metal compound (1) is a metal compound (M1) containing at least one metal element M1 selected from
Of the components used in the step (1), at least one component other than the solvent has an oxygen atom (that is, when the compound (3) is used, the compound (1), the compound (2) and the compound (3 ) Has an oxygen atom, and when compound (3) is not used, at least one of compound (1) and compound (2) has an oxygen atom)
It is characterized by that.
本発明の燃料電池用電極触媒(以下、単に「触媒」ともいう)は、上述した本発明の燃料電池用電極触媒の製造方法により製造されることを特徴としている。また、本発明の触媒は、上述した本発明の熱処理物からなっていてもよい。 [Electrocatalyst for fuel cell]
The fuel cell electrode catalyst of the present invention (hereinafter also simply referred to as “catalyst”) is characterized by being produced by the above-described method for producing a fuel cell electrode catalyst of the present invention. Moreover, the catalyst of this invention may consist of the heat-processing thing of this invention mentioned above.
xの範囲は、より好ましくは0.15≦x≦9.0、さらに好ましくは0.2≦x≦8.0であり、特に好ましくは1.0≦x≦7.0であり、
yの範囲は、より好ましくは0.01≦y≦2.0、さらに好ましくは0.02≦y≦1.8であり、特に好ましくは0.03≦y≦1.5であり、
zの範囲は、より好ましくは0.05≦z≦5.0であり、さらに好ましくは0.1≦z≦4.0であり、特に好ましくは0.2≦z≦3.5であり、
aの範囲は、より好ましくは0.001≦a≦1であり、さらに好ましくは0.001≦a≦0.5であり、特に好ましくは0.001≦a≦0.2であり、
bの範囲は、より好ましくは0.0001≦b≦2であり、さらに好ましくは0.001≦b≦1であり、特に好ましくは0.001≦b≦0.2である。 Because the activity of the electrocatalyst is high,
The range of x is more preferably 0.15 ≦ x ≦ 9.0, still more preferably 0.2 ≦ x ≦ 8.0, particularly preferably 1.0 ≦ x ≦ 7.0,
The range of y is more preferably 0.01 ≦ y ≦ 2.0, further preferably 0.02 ≦ y ≦ 1.8, particularly preferably 0.03 ≦ y ≦ 1.5,
The range of z is more preferably 0.05 ≦ z ≦ 5.0, further preferably 0.1 ≦ z ≦ 4.0, and particularly preferably 0.2 ≦ z ≦ 3.5.
The range of a is more preferably 0.001 ≦ a ≦ 1, more preferably 0.001 ≦ a ≦ 0.5, and particularly preferably 0.001 ≦ a ≦ 0.2.
The range of b is more preferably 0.0001 ≦ b ≦ 2, more preferably 0.001 ≦ b ≦ 1, and particularly preferably 0.001 ≦ b ≦ 0.2.
電子伝導性物質であるカーボンに分散させた触媒が1質量%となるように、該触媒及びカーボンを溶剤中に入れ、超音波で攪拌し懸濁液を得る。なお、カーボンとしては、カーボンブラック(比表面積:100~300m2/g)(例えばキャボット社製 VULCAN(登録商標) XC72)を用い、触媒とカーボンとが質量比で95:5になるように分散させる。また、溶剤としては、イソプロピルアルコール:水(質量比)=2:1を用いる。 [Measurement method (A):
The catalyst and carbon are placed in a solvent so that the amount of the catalyst dispersed in carbon, which is an electron conductive material, is 1% by mass, and stirred with ultrasonic waves to obtain a suspension. As carbon, carbon black (specific surface area: 100 to 300 m 2 / g) (for example, VULCAN (registered trademark) XC72 manufactured by Cabot Corporation) is used, and the catalyst and carbon are dispersed so that the mass ratio is 95: 5. Let As the solvent, isopropyl alcohol: water (mass ratio) = 2: 1 is used.
本発明において、酸素還元電流密度は、以下のとおり求めることができる。 Thus, using the obtained electrode, a reversible hydrogen electrode in a sulfuric acid aqueous solution of the same concentration at a temperature of 30 ° C. in a 0.5 mol / L sulfuric acid aqueous solution in an oxygen atmosphere and a nitrogen atmosphere was used as a reference electrode. When a current-potential curve is measured by polarization at a potential scanning speed of 5 mV / sec, a difference of 0.2 μA / cm 2 or more appears between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere. The starting potential is defined as the oxygen reduction starting potential. ]
In the present invention, the oxygen reduction current density can be determined as follows.
本発明の触媒は、白金触媒の代替触媒として使用することができる。 [Usage]
The catalyst of the present invention can be used as an alternative catalyst for a platinum catalyst.
本発明の燃料電池を備えることができる前記物品の具体例としては、ビル、家屋、テント等の建築物、蛍光灯、LED等、有機EL、街灯、屋内照明、信号機等の照明器具、機械、車両そのものを含む自動車用機器、家電製品、農業機器、電子機器、携帯電話等を含む携帯情報端末、美容機材、可搬式工具、風呂用品トイレ用品等の衛生機材、家具、玩具、装飾品、掲示板、クーラーボックス、屋外発電機などのアウトドア用品、教材、造花、オブジェ、心臓ペースメーカー用電源、ペルチェ素子を備えた加熱および冷却器用の電源が挙げられる。 <Specific example of article provided with fuel cell of the present invention>
Specific examples of the article that can include the fuel cell of the present invention include buildings, houses, buildings such as tents, fluorescent lamps, LEDs, etc., organic EL, street lamps, indoor lighting, lighting fixtures such as traffic lights, machines, Automotive equipment including the vehicle itself, home appliances, agricultural equipment, electronic equipment, portable information terminals including mobile phones, beauty equipment, portable tools, sanitary equipment such as bathroom accessories, furniture, toys, decorations, bulletin boards , Outdoor supplies such as cooler boxes, outdoor generators, teaching materials, artificial flowers, objects, power supplies for cardiac pacemakers, power supplies for heating and cooling devices with Peltier elements.
1.粉末X線回折測定
理学電機株式会社製 ロータフレックスを用いて、試料の粉末X線回折を行った。 [Analysis method]
1. Powder X-ray diffraction measurement Powder X-ray diffraction of the sample was performed using a rotor flex made by Rigaku Corporation.
走査軸:θ/2θ
測定範囲(2θ):10.00°~89.98°
測定モード:FT
読込幅:0.02°
サンプリング時間:0.70秒
DS、SS、RS:0.5°、0.5°、0.15mm
ゴニオメーター半径:185mm
各試料の粉末X線回折における回折線ピークの本数は、信号(S)とノイズ(N)の比(S/N)が2以上で検出できるシグナルを1つのピークとしてみなして数えた。 X-ray output (Cu-Kα): 50 kV, 180 mA
Scanning axis: θ / 2θ
Measurement range (2θ): 10.00 ° to 89.98 °
Measurement mode: FT
Reading width: 0.02 °
Sampling time: 0.70 seconds DS, SS, RS: 0.5 °, 0.5 °, 0.15 mm
Goniometer radius: 185mm
The number of diffraction line peaks in powder X-ray diffraction of each sample was counted by regarding a signal that can be detected at a ratio (S / N) of signal (S) to noise (N) of 2 or more as one peak.
<炭素、硫黄>
試料約0.01gを量り取り、炭素硫黄分析装置(堀場製作所製EMIA-920V)にて測定を行った。 2. Elemental analysis <carbon, sulfur>
About 0.01 g of a sample was weighed and measured with a carbon sulfur analyzer (EMIA-920V manufactured by Horiba, Ltd.).
試料約0.01gを量り取り、Niカプセルに試料を封入して、酸素窒素分析装置(LECO製TC600)にて測定を行った。 <Nitrogen, oxygen>
About 0.01 g of a sample was weighed, sealed in a Ni capsule, and measured with an oxygen-nitrogen analyzer (TC600 manufactured by LECO).
試料約0.1gを石英ビーカーに量り取り、硫酸,硝酸およびフッ酸を用いて試料を完全に加熱分解した。冷却後、この溶液を100mlに定容し、さらに適宜希釈し、ICP-OES(SII社製VISTA-PRO)またはICP-MS(Agilent社製HP7500)を用いて定量を行った。 <Metal>
About 0.1 g of the sample was weighed into a quartz beaker, and the sample was completely thermally decomposed using sulfuric acid, nitric acid and hydrofluoric acid. After cooling, the solution was made up to a volume of 100 ml, further diluted as appropriate, and quantified using ICP-OES (VISA-PRO by SII) or ICP-MS (HP7500 by Agilent).
試料数mgを、酸素気流下、水蒸気を通気しながら燃焼分解した。発生したガスを10mM Na2CO3(過酸化水素を含む。補正用標準Br‐:5ppm)に吸収させ、イオンクロマトグラフィーでフッ素の量を測定した。 <Fluorine>
A few mg of the sample was combusted and decomposed while flowing water vapor in an oxygen stream. The generated gas was absorbed into 10 mM Na 2 CO 3 (containing hydrogen peroxide. Correction standard Br—: 5 ppm), and the amount of fluorine was measured by ion chromatography.
試料燃焼装置:AQF-100((株)三菱化学アナリテック社製)
燃焼管温度:950℃(試料ボード移動による昇温分解)
イオンクロマトグラフィー測定条件
測定装置:DIONEX DX-500
溶離液:1.8mM Na2CO3+1.7mM NaHCO3
カラム(温度):ShodexSI-90(室温)
流速:1.0ml/分
注入量:25μl
検出器:電気伝導度検出器
サプレッサー:DIONEX ASRS-300
<ホウ素>
試料数十mgを、リン酸を加えた後、硫酸を加えて硫酸の白煙を発生するまで加熱し、放冷した。その後、硝酸添加→加熱→放冷の操作を数回繰り返した。これらの操作後の試料をポリ容器中で純水で50mlに定容後、定容物を(ただし、沈殿物が生じた場合には上澄み液を)純水で10倍希釈した。その後、ICP発光分析でホウ素量を測定した。 Combustion decomposition conditions:
Sample combustion apparatus: AQF-100 (Mitsubishi Chemical Analytech Co., Ltd.)
Combustion tube temperature: 950 ° C (temperature decomposition by moving the sample board)
Ion chromatography measurement conditions Measuring device: DIONEX DX-500
Eluent: 1.8 mM Na 2 CO 3 +1.7 mM NaHCO 3
Column (temperature): ShodexSI-90 (room temperature)
Flow rate: 1.0 ml / min Injection volume: 25 μl
Detector: Electrical conductivity detector Suppressor: DIONEX ASRS-300
<Boron>
After adding phosphoric acid, several tens mg of the sample was heated until sulfuric acid was added and white smoke of sulfuric acid was generated, and the mixture was allowed to cool. Thereafter, the operation of adding nitric acid → heating → cooling was repeated several times. The sample after these operations was made up to a volume of 50 ml with pure water in a plastic container, and the constant volume was diluted 10 times with pure water (however, when the precipitate was formed, the supernatant liquid). Thereafter, the amount of boron was measured by ICP emission analysis.
試料約0.02gを、硫酸を加え、硫酸の白煙が発生するまで加熱し、放冷後、硝酸を加え、完全分解するまで、硝酸添加→加熱→放冷の操作を繰り返した。これらの操作後の試料をポリ容器中で純水で100mlに定容した。白濁が認めた場合には、白濁が認められなくなるまでフッ酸を添加した。定容物を純水でさらに50倍に希釈し、ICP発光分析でリン量を測定した。 <Phosphorus>
About 0.02 g of the sample was added with sulfuric acid and heated until white smoke of sulfuric acid was generated. After standing to cool, nitric acid was added and the operation of adding nitric acid → heating → cooling was repeated until complete decomposition. The sample after these operations was made up to 100 ml with pure water in a plastic container. When cloudiness was observed, hydrofluoric acid was added until cloudiness was not observed. The fixed volume was further diluted 50 times with pure water, and the amount of phosphorus was measured by ICP emission analysis.
島津製作所株式会社製 マイクロメリティクス ジェミニ2360を用いてBET比表面積を測定した。前処理時間、前処理温度は、それぞれ30分、200℃に設定した。 3. BET specific surface area measurement BET specific surface area was measured using Micromeritics Gemini 2360 manufactured by Shimadzu Corporation. The pretreatment time and pretreatment temperature were set at 30 ° C. and 200 ° C., respectively.
1.触媒の製造
ビーカーに、アセチルアセトン2.60g(25.94mmol)を入れ、これを攪拌しながらスズ(IV)イソプロポキシド6.25g(17.59mmol)を加え、さらに酢酸28mlを2分間かけて滴下し、スズ溶液(1)を調製した。 [Example 1]
1. Production of catalyst 2.60 g (25.94 mmol) of acetylacetone was placed in a beaker, and 6.25 g (17.59 mmol) of tin (IV) isopropoxide was added thereto while stirring, and 28 ml of acetic acid was further added dropwise over 2 minutes. A tin solution (1) was prepared.
触媒(1)95mgとカーボン(キャボット社製 VULCAN(登録商標) XC72)5mgとを、イソプロピルアルコール:純水=2:1の質量比で混合した溶液10gに入れ、超音波で撹拌、懸濁して混合した。この混合物30μlをグラッシーカーボン電極(東海カーボン社製、直径:6mm)に塗布し、120℃で5分間乾燥して、カーボン電極表面に1.0mg以上の燃料電池用触媒層が形成した。さらに、燃料電池用触媒層の上に5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)を10倍にイソプロピルアルコールで希釈したもの10μlを塗布し、120℃で1時間乾燥し、燃料電池用電極(1)を得た。 2. Production of Fuel Cell Electrode 95 mg of the catalyst (1) and 5 mg of carbon (VULCAN (registered trademark) XC72) manufactured by Cabot Corporation were mixed in 10 g of a solution having a mass ratio of isopropyl alcohol: pure water = 2: 1. And suspended and mixed. 30 μl of this mixture was applied to a glassy carbon electrode (Tokai Carbon Co., Ltd., diameter: 6 mm) and dried at 120 ° C. for 5 minutes to form a fuel cell catalyst layer of 1.0 mg or more on the surface of the carbon electrode. Further, 10 μl of a 5% Nafion (registered trademark) solution (DE521, DuPont) diluted 10-fold with isopropyl alcohol was applied on the fuel cell catalyst layer, and dried at 120 ° C. for 1 hour. A fuel cell electrode (1) was obtained.
作製した燃料電池用電極(1)を、酸素雰囲気および窒素雰囲気で、0.5mol/Lの硫酸水溶液中、30℃、5mV/秒の電位走査速度で分極し、それぞれ電流-電位曲線を測定した。その際、同濃度の硫酸水溶液中での可逆水素電極を参照電極とした。 3. Evaluation of oxygen reduction ability The produced fuel cell electrode (1) was polarized in an oxygen atmosphere and a nitrogen atmosphere in a 0.5 mol / L sulfuric acid aqueous solution at 30 ° C. and a potential scanning rate of 5 mV / sec. A potential curve was measured. At that time, a reversible hydrogen electrode in an aqueous sulfuric acid solution having the same concentration was used as a reference electrode.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例1と同様の操作を行い、粉末状の触媒(2)281mgを得た。なお、この過程で得られた焼成用粉末の重量は12.3gであった。 [Example 2]
1. Production of catalyst The same operation as in Example 1 was conducted except that a NAFION (registered trademark) solution was not used, to obtain 281 mg of a powdery catalyst (2). The weight of the powder for firing obtained in this process was 12.3 g.
触媒(1)95mgに替えて触媒(2)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(2)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (2) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (2) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
酢酸鉄(II)を用いなかったこと以外は実施例1と同様の操作を行い、粉末状の触媒(3)224mgを得た。なお、この過程で得られた焼成用粉末の重量は14.7gであった。 [Example 3]
1. Production of catalyst The same operation as in Example 1 was carried out except that iron (II) acetate was not used, to obtain 224 mg of a powdery catalyst (3). The weight of the powder for firing obtained in this process was 14.7 g.
触媒(1)95mgに替えて触媒(3)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(3)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (3) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (3) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例3と同様の操作を行い、粉末状の触媒(4)224mgを得た。なお、この過程で得られた焼成用粉末の重量は14.7gであった。 [Example 4]
1. Production of catalyst The same operation as in Example 3 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 224 mg of a powdery catalyst (4). The weight of the powder for firing obtained in this process was 14.7 g.
触媒(1)95mgに替えて触媒(4)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(4)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (4) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (4) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸16mlを入れ、これを攪拌しながらスズ(II)アセチルアセトナート5.58g(17.59mmol)を加え、スズ溶液(5)を調製した。 [Example 5]
1. Production of catalyst 16 ml of acetic acid was placed in a beaker, and 5.58 g (17.59 mmol) of tin (II) acetylacetonate was added thereto while stirring to prepare a tin solution (5).
触媒(1)95mgに替えて触媒(5)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(5)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (5) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (5) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸70mlを入れ、これを攪拌しながらスズ(II)アセチルアセトナート5.58g(17.59mmol)を加え、スズ溶液(6)を調製した。 [Example 6]
1. Production of catalyst 70 ml of acetic acid was placed in a beaker, and 5.58 g (17.59 mmol) of tin (II) acetylacetonate was added thereto while stirring to prepare a tin solution (6).
触媒(1)95mgに替えて触媒(6)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(6)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (6) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (6) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール25mlを入れ、これを撹拌しながら四塩化スズ5.33g(20mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)12.5ml、酢酸鉄(II)355mg(2.049mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(7)を得た。 [Example 7]
1. Production of catalyst In a beaker, 25 ml of methanol was added, and while stirring, 5.33 g (20 mmol) of tin tetrachloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 355 mg (2.049 mmol) was added sequentially. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (7).
触媒(1)95mgに替えて触媒(7)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(7)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (7) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (7) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール33mlを入れ、これを撹拌しながら四塩化スズ5.33g(20mmol)、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(8)を得た。 [Example 8]
1. Production of catalyst 33 ml of methanol was placed in a beaker, and 5.33 g (20 mmol) of tin tetrachloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (8).
触媒(1)95mgに替えて触媒(8)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(8)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (8) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (8) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール50mlを入れ、これを撹拌しながら二塩化銅2.75g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)10ml、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(9)を得た。 [Example 9]
1. Production of catalyst In a beaker, 50 ml of methanol was added, and while stirring, 2.75 g (20.45 mmol) of copper dichloride, 10 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 355 mg (2.045 mmol) was added sequentially. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (9).
触媒(1)95mgに替えて触媒(9)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(9)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (9) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (9) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液の代わりにテトラフルオロホウ酸テトラエチルアンモニウムを用いたこと以外は実施例9と同様の操作を行い、粉末状の触媒(10)667mgを得た。なお、この過程で得られた焼成用粉末の重量は3.00gであった。 [Example 10]
1. Production of catalyst The same operation as in Example 9 was carried out except that tetraethylammonium tetrafluoroborate was used in place of the NAFION (registered trademark) solution to obtain 667 mg of a powdery catalyst (10). The weight of the powder for firing obtained in this process was 3.00 g.
触媒(1)95mgに替えて触媒(10)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(10)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (10) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (10) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液の代わりにヘキサフルオロリン酸テトラメチルアンモニウムを用いたこと以外は実施例9と同様の操作を行い、粉末状の触媒(11)708mgを得た。なお、この過程で得られた焼成用粉末の重量は2.89gであった。 [Example 11]
1. Production of catalyst The same operation as in Example 9 was carried out except that tetramethylammonium hexafluorophosphate was used instead of the NAFION (registered trademark) solution to obtain 708 mg of a powdery catalyst (11). The weight of the powder for firing obtained in this process was 2.89 g.
触媒(1)95mgに替えて触媒(11)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(11)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (11) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (11) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例9と同様の操作を行い、粉末状の触媒(12)682mgを得た。なお、この過程で得られた焼成用粉末の重量は3.07gであった。 [Example 12]
1. Production of catalyst The same operation as in Example 9 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 682 mg of a powdery catalyst (12). The weight of the powder for firing obtained in this process was 3.07 g.
触媒(1)95mgに替えて触媒(12)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(12)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (12) was produced in the same manner as in Example 1 except that 95 mg of catalyst (12) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール50mlを入れ、これを撹拌しながら三塩化セリウム5.05g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)12.5ml、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(13)を得た。 [Example 13]
1. Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring this, 5.05 g (20.45 mmol) of cerium trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid 355 mg (2.045 mmol) of iron (II) was added sequentially. Pyrazinecarboxylic acid (10.15 g, 81.80 mmol) was added little by little to the resulting solution, followed by stirring for 3 hours to obtain a catalyst precursor solution (13).
触媒(1)95mgに替えて触媒(13)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(13)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (13) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (13) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例13と同様の操作を行い、粉末状の触媒(14)682mgを得た。なお、この過程で得られた焼成用粉末の重量は3.07gであった。 [Example 14]
1. Production of catalyst The same operation as in Example 13 was carried out except that the NAFION (registered trademark) solution was not used, to obtain 682 mg of a powdery catalyst (14). The weight of the powder for firing obtained in this process was 3.07 g.
触媒(1)95mgに替えて触媒(14)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(14)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (14) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (14) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール27mlを入れ、これを撹拌しながら三塩化アルミニウム3.45g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)12.5ml、酢酸鉄(II)357mg(2.049mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.16g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(15)を得た。 [Example 15]
1. Preparation of catalyst In a beaker, 27 ml of methanol was added, and while stirring, 3.45 g (20.45 mmol) of aluminum trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid Iron (II) 357 mg (2.049 mmol) was sequentially added. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (15).
触媒(1)95mgに替えて触媒(15)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(15)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (15) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (15) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール37mlを入れ、これを撹拌しながら三塩化アルミニウム3.45g(20.45mmol)、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.16g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(16)を得た。 [Example 16]
1. Production of catalyst 37 ml of methanol was placed in a beaker, and 3.45 g (20.45 mmol) of aluminum trichloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (16).
触媒(1)95mgに替えて触媒(16)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(16)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (16) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (16) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール45mlを入れ、これを撹拌しながら四塩化タングステン6.66g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)12.5ml、酢酸鉄(II)355mg(2.049mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(17)を得た。 [Example 17]
1. Preparation of catalyst In a beaker, 45 ml of methanol was added, and while stirring, 6.66 g (20.45 mmol) of tungsten tetrachloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid Iron (II) 355 mg (2.049 mmol) was sequentially added. After adding 10.15 g (81.80 mmol) of pyrazinecarboxylic acid little by little to the resulting solution, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (17).
触媒(1)95mgに替えて触媒(17)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(17)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (17) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (17) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール33mlを入れ、これを撹拌しながら四塩化タングステン6.66g(20.45mmol)、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.16g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(18)を得た。 [Example 18]
1. Production of catalyst 33 ml of methanol was placed in a beaker, and 6.66 g (20.45 mmol) of tungsten tetrachloride and 355 mg (2.045 mmol) of iron (II) acetate were sequentially added thereto while stirring. After adding 10.16 g (81.80 mmol) of pyrazinecarboxylic acid to the resulting solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (18).
触媒(1)95mgに替えて触媒(18)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(18)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (18) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (18) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール50mlを入れ、これを撹拌しながら三塩化イットリウム3.88g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)12.5ml、酢酸鉄(II)355mg(2.045mmol)を順次加えた。得られた溶液にピラジンカルボン酸10.15g(81.80mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(19)を得た。 [Example 19]
1. Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring this, 3.88 g (20.45 mmol) of yttrium trichloride, 12.5 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), acetic acid 355 mg (2.045 mmol) of iron (II) was added sequentially. Pyrazinecarboxylic acid (10.15 g, 81.80 mmol) was added little by little to the resulting solution, followed by stirring for 3 hours to obtain a catalyst precursor solution (19).
触媒(1)95mgに替えて触媒(19)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(19)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (19) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (19) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例19と同様の操作を行い、粉末状の触媒(20)597mgを得た。なお、この過程で得られた焼成用粉末の重量は9.61gであった。 [Example 20]
1. Production of catalyst The same operation as in Example 19 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 597 mg of a powdery catalyst (20). The weight of the powder for firing obtained in this process was 9.61 g.
触媒(1)95mgに替えて触媒(20)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(20)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (20) was produced in the same manner as in Example 1 except that 95 mg of catalyst (20) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール50mlを入れ、これを撹拌しながら二塩化ニッケル5.31g(20.45mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)25ml、酢酸鉄(II)710mg(4.09mmol)を順次加えた。得られた溶液にピラジンカルボン酸20.30g(163.6mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(21)を得た。 [Example 21]
1. Preparation of catalyst In a beaker, 50 ml of methanol was added, and while stirring, 5.31 g (20.45 mmol) of nickel dichloride, 25 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 710 mg (4.09 mmol) was added sequentially. After adding 20.30 g (163.6 mmol) of pyrazinecarboxylic acid to the obtained solution little by little, the mixture was stirred for 3 hours to obtain a catalyst precursor solution (21).
触媒(1)95mgに替えて触媒(21)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(21)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (21) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (21) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール100mlを入れ、これを撹拌しながら二塩化ニッケル5.30g(40.90mmol)、酢酸鉄(II)710mg(4.09mmol)を順次加えた。得られた溶液にピラジンカルボン酸20.30g(163.6mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(22)を得た。 [Example 22]
1. Production of
触媒(1)95mgに替えて触媒(22)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(22)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (22) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (22) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸58mlを入れ、これを撹拌しながらクロム(III)アセチルアセトナート6.14g(17.54mmol)を加え、クロム溶液(23)を調製した。 [Example 23]
1. Production of catalyst Into a beaker, 58 ml of acetic acid was added, and 6.14 g (17.54 mmol) of chromium (III) acetylacetonate was added with stirring to prepare a chromium solution (23).
触媒(1)95mgに替えて触媒(23)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(23)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (23) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (23) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例23と同様の操作を行い、粉末状の触媒(24)262mgを得た。なお、この過程で得られた焼成用粉末の重量は13.4gであった。 [Example 24]
1. Production of catalyst The same operation as in Example 23 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 262 mg of a powdery catalyst (24). The weight of the powder for firing obtained in this process was 13.4 g.
触媒(1)95mgに替えて触媒(24)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(24)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (24) was produced in the same manner as in Example 1 except that 95 mg of catalyst (24) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸58mlを入れ、これを撹拌しながら鉄(III)アセチルアセトナート6.21g(17.59mmol)を加え、鉄溶液(25)を調製した。 [Example 25]
1. Production of catalyst Into a beaker, 58 ml of acetic acid was added, and 6.21 g (17.59 mmol) of iron (III) acetylacetonate was added with stirring to prepare an iron solution (25).
触媒(1)95mgに替えて触媒(25)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(25)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (25) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (25) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例25と同様の操作を行い、粉末状の触媒(26)262mgを得た。なお、この過程で得られた焼成用粉末の重量は10.6gであった。 [Example 26]
1. Production of catalyst The same operation as in Example 25 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 262 mg of a powdery catalyst (26). The weight of the powder for firing obtained in this process was 10.6 g.
触媒(1)95mgに替えて触媒(26)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(26)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (26) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (26) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸128mlを入れ、これを撹拌しながらコバルト(II)アセチルアセトナート水和物5.16g(17.59mmol)を加え、コバルト溶液(27)を調製した。 [Example 27]
1. Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 5.16 g (17.59 mmol) of cobalt (II) acetylacetonate hydrate was added thereto while stirring to prepare a cobalt solution (27).
触媒(1)95mgに替えて触媒(27)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(27)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (27) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (27) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例27と同様の操作を行い、粉末状の触媒(28)306mgを得た。なお、この過程で得られた焼成用粉末の重量は10.3gであった。 [Example 28]
1. Production of catalyst The same operation as in Example 27 was carried out except that the NAFION (registered trademark) solution was not used, to obtain 306 mg of a powdery catalyst (28). In addition, the weight of the powder for baking obtained in this process was 10.3 g.
触媒(1)95mgに替えて触媒(28)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(28)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Ability A fuel cell electrode (28) was produced in the same manner as in Example 1 except that 95 mg of catalyst (28) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸128mlを入れ、これを撹拌しながらマンガン(III)アセチルアセトナート6.20g(17.59mmol)を加え、マンガン溶液(29)を調製した。 [Example 29]
1. Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 6.20 g (17.59 mmol) of manganese (III) acetylacetonate was added with stirring to prepare a manganese solution (29).
触媒(1)95mgに替えて触媒(29)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(29)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (29) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (29) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例29と同様の操作を行い、粉末状の触媒(30)315mgを得た。なお、この過程で得られた焼成用粉末の重量は9.76gであった。 [Example 30]
1. Production of catalyst The same operation as in Example 29 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 315 mg of a powdery catalyst (30). The weight of the powder for firing obtained in this process was 9.76 g.
触媒(1)95mgに替えて触媒(30)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(30)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (30) was produced in the same manner as in Example 1 except that 95 mg of catalyst (30) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、酢酸128mlを入れ、これを撹拌しながらストロンチウムビスアセチルアセトナート5.03g(17.59mmol)を加え、ストロンチウム溶液(31)を調製した。 [Example 31]
1. Production of catalyst Into a beaker, 128 ml of acetic acid was added, and 5.03 g (17.59 mmol) of strontium bisacetylacetonate was added with stirring to prepare a strontium solution (31).
触媒(1)95mgに替えて触媒(31)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(31)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (31) was produced in the same manner as in Example 1 except that 95 mg of catalyst (31) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ナフィオン(NAFION(登録商標))溶液を用いなかったこと以外は実施例31と同様の操作を行い、粉末状の触媒(32)337mgを得た。なお、この過程で得られた焼成用粉末の重量は10.0gであった。 [Example 32]
1. Production of catalyst The same operation as in Example 31 was carried out except that a NAFION (registered trademark) solution was not used, to obtain 337 mg of a powdery catalyst (32). The weight of the powder for firing obtained in this process was 10.0 g.
触媒(1)95mgに替えて触媒(32)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(32)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (32) was produced in the same manner as in Example 1 except that 95 mg of catalyst (32) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
ビーカーに、メタノール100mlを入れ、これを撹拌しながら二塩化銅5.50g(40.9mmol)、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)25ml、酢酸鉄(II)711mg(4.09mmol)を順次加えた。得られた溶液にピラジンカルボン酸15.23g(121.6mmol)を少量ずつ加えた後、3時間の攪拌を行い触媒前駆体溶液(33)を得た。なおこの攪拌中に、時間の経過とともに沈殿物が生じた。 [Example 33]
1. Preparation of catalyst In a beaker, 100 ml of methanol was added, and while stirring, 5.50 g (40.9 mmol) of copper dichloride, 25 ml of 5% Nafion (NAFION®) solution (DE521, DuPont), iron acetate ( II) 711 mg (4.09 mmol) was added sequentially. To the obtained solution, 15.23 g (121.6 mmol) of pyrazinecarboxylic acid was added little by little, followed by stirring for 3 hours to obtain a catalyst precursor solution (33). During this stirring, a precipitate was formed over time.
触媒(1)95mgに替えて触媒(33)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(33)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (33) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (33) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
2gの前記焼成用粉末(33)を、ロータリーキルン炉に水素ガスを4体積%含む窒素ガスを125ml/分の速度で流しながら、昇温速度10℃/分で1050℃まで加熱し、1050℃で1.5時間焼成し、自然冷却することにより、粉末状の触媒(34)778mgを得た。 [Example 34]
2 g of the powder for firing (33) was heated to 1050 ° C. at a heating rate of 10 ° C./min while flowing nitrogen gas containing 4% by volume of hydrogen gas at a rate of 125 ml / min in a rotary kiln furnace. By baking for 1.5 hours and naturally cooling, 778 mg of a powdery catalyst (34) was obtained.
触媒(1)95mgに替えて触媒(34)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(34)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (34) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (34) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
塩化銅の代わりに二塩化銅1.37g(10.2mmol)、三塩化スズ1.94g(10.2mmol)を用い、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)の量を12.5mlに変更したこと以外は実施例9と同様の操作を行い、粉末状の触媒(35)337mgを得た。なお、この過程で得られた焼成用粉末の重量は4.68gであった。 [Example 35]
1. Production of catalyst 1.37 g (10.2 mmol) of copper dichloride and 1.94 g (10.2 mmol) of tin trichloride were used instead of copper chloride, and a 5% NAFION (registered trademark) solution (DE521, DuPont) ) Was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 337 mg of a powdery catalyst (35). In addition, the weight of the powder for baking obtained in this process was 4.68 g.
触媒(1)95mgに替えて触媒(35)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(35)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (35) was produced in the same manner as in Example 1 except that 95 mg of catalyst (35) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
二塩化銅の量を1.81g(13.5mmol)に変更し、三塩化スズの量を1.28g(6.75mmol)に変更したこと以外は実施例35と同様の操作を行い、粉末状の触媒(36)327mgを得た。なお、この過程で得られた焼成用粉末の重量は3.73gであった。 [Example 36]
1. Production of catalyst The same procedure as in Example 35 was performed, except that the amount of copper dichloride was changed to 1.81 g (13.5 mmol) and the amount of tin trichloride was changed to 1.28 g (6.75 mmol). 327 mg of a powdery catalyst (36) was obtained. In addition, the weight of the powder for baking obtained in this process was 3.73g.
触媒(1)95mgに替えて触媒(36)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(36)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (36) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (36) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
二塩化銅の量を0.907g(6.75mmol)に変更し、三塩化スズの量を2.56g(13.5mmol)に変更したこと以外は実施例35と同様の操作を行い、粉末状の触媒(37)275mgを得た。なお、この過程で得られた焼成用粉末の重量は5.10gであった。 [Example 37]
1. Production of catalyst The same operation as in Example 35 was performed except that the amount of copper dichloride was changed to 0.907 g (6.75 mmol) and the amount of tin trichloride was changed to 2.56 g (13.5 mmol). 275 mg of a powdery catalyst (37) was obtained. The weight of the powder for firing obtained in this process was 5.10 g.
触媒(1)95mgに替えて触媒(37)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(37)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (37) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (37) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
塩化銅の代わりに二塩化銅1.37g(10.2mmol)、四塩化チタン 1.94g(10.2mmol)を用い、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)の量を12.5mlに変更したこと以外は実施例9と同様の操作を行い、粉末状の触媒(38)426mgを得た。なお、この過程で得られた焼成用粉末(33)の重量は3.52gであった。 [Example 38]
1. Production of catalyst Using 1.37 g (10.2 mmol) of copper dichloride and 1.94 g (10.2 mmol) of titanium tetrachloride instead of copper chloride, a 5% NAFION (registered trademark) solution (DE521, DuPont) ) Was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 426 mg of a powdery catalyst (38). The weight of the powder for firing (33) obtained in this process was 3.52 g.
触媒(1)95mgに替えて触媒(38)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(38)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (38) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (38) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
四塩化チタンの量を1.28g(6.75mmol)に変更し、二塩化銅の量を1.81g(13.5mmol)に変更したこと以外は実施例38と同様の操作を行い、粉末状の触媒(39)425mgを得た。なお、この過程で得られた焼成用粉末(39)の重量は3.57gであった。 [Example 39]
1. Production of catalyst The same operation as in Example 38 was performed except that the amount of titanium tetrachloride was changed to 1.28 g (6.75 mmol) and the amount of copper dichloride was changed to 1.81 g (13.5 mmol). 425 mg of a powdery catalyst (39) was obtained. The weight of the firing powder (39) obtained in this process was 3.57 g.
触媒(1)95mgに替えて触媒(39)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(39)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (39) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (39) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
実施例39における焼成用粉末(39)の製造過程と同様の操作を行い、3.57gの焼成用粉末(40)を得た。 [Example 40]
1. Production of Catalyst The same operation as in the production process of the firing powder (39) in Example 39 was performed to obtain 3.57 g of the firing powder (40).
触媒(1)95mgに替えて触媒(40)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(40)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (40) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (40) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
四塩化チタンの量を0.388g(2.04mmol)に変更し、二塩化銅の量を0.475g(18.4mmol)に変更したこと以外は実施例38と同様の操作を行い、粉末状の触媒(41)313mgを得た。なお、この過程で得られた焼成用粉末(41)の重量は3.39gであった。 [Example 41]
1. Production of catalyst The same operation as in Example 38 was performed except that the amount of titanium tetrachloride was changed to 0.388 g (2.04 mmol) and the amount of copper dichloride was changed to 0.475 g (18.4 mmol). 313 mg of a powdery catalyst (41) was obtained. The weight of the firing powder (41) obtained in this process was 3.39 g.
触媒(1)95mgに替えて触媒(41)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(41)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (41) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (41) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
ビーカーに、酢酸8mlを入れ、これを攪拌しながらアセチルアセトン2.60g(25.9mmol)と、ジルコニアブトキシド7.94g(17.6mmol)を加え、ジルコニウム溶液(42)を調製した。 [Example 42]
Into a beaker, 8 ml of acetic acid was added, and 2.60 g (25.9 mmol) of acetylacetone and 7.94 g (17.6 mmol) of zirconia butoxide were added with stirring to prepare a zirconium solution (42).
触媒(1)95mgに替えて触媒(42)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(42)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (42) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (42) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
ビーカーに、酢酸8mlを入れ、これを攪拌しながらアセチルアセトン1.30g(13.0mmol)と、ジルコニアブトキシド3.92g(10.2mmol)を加え、ジルコニウム溶液(43)を調製した。 [Example 43]
8 ml of acetic acid was put into a beaker, and 1.30 g (13.0 mmol) of acetylacetone and 3.92 g (10.2 mmol) of zirconia butoxide were added while stirring the mixture to prepare a zirconium solution (43).
触媒(1)95mgに替えて触媒(43)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(43)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (43) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (43) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
塩化銅の代わりに四塩化チタン1.94g(10.2mmol)、三塩化スズ1.94g(10.2mmol)を用い、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)の量を12.5mlに変更したこと以外は実施例9と同様の操作を行い、粉末状の触媒(44)358mgを得た。なお、この過程で得られた焼成用粉末(44)の重量は5.00gであった。 [Example 44]
1. Preparation of catalyst 5% Nafion (registered trademark) solution (DE521, DuPont) using 1.94 g (10.2 mmol) of titanium tetrachloride and 1.94 g (10.2 mmol) of tin trichloride instead of copper chloride ) Was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 358 mg of a powdery catalyst (44). The weight of the firing powder (44) obtained in this process was 5.00 g.
触媒(1)95mgに替えて触媒(44)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(44)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Ability A fuel cell electrode (44) was produced in the same manner as in Example 1 except that 95 mg of catalyst (44) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
塩化銅の代わりに二塩化銅1.37g(10.2mmol)、五塩化タンタル5.66g(10.2mmol)を用い、5%ナフィオン(NAFION(登録商標))溶液(DE521、デュポン社)の量を12.5mlに変更したこと以外は実施例9と同様の操作を行い、粉末状の触媒(45)714mgを得た。なお、この過程で得られた焼成用粉末の重量は7.16gであった。 [Example 45]
1. Preparation of catalyst 1.37 g (10.2 mmol) of copper dichloride and 5.66 g (10.2 mmol) of tantalum pentachloride were used instead of copper chloride, and a 5% NAFION (registered trademark) solution (DE521, DuPont) ) Was changed to 12.5 ml, and the same operation as in Example 9 was performed to obtain 714 mg of a powdery catalyst (45). The weight of the firing powder obtained in this process was 7.16 g.
触媒(1)95mgに替えて触媒(45)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(45)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (45) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (45) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
二塩化銅の量を1.81g(13.5mmol)に変更し、五塩化タンタルの量を2.42g(6.45mmol)に変更したこと以外は実施例45と同様の操作を行い、粉末状の触媒(46)628mgを得た。なお、この過程で得られた焼成用粉末(46)の重量は4.27gであった。 [Example 46]
1. Production of catalyst The same procedure as in Example 45 was performed, except that the amount of copper dichloride was changed to 1.81 g (13.5 mmol) and the amount of tantalum pentachloride was changed to 2.42 g (6.45 mmol). 628 mg of a powdery catalyst (46) was obtained. The weight of the powder for firing (46) obtained in this process was 4.27 g.
触媒(1)95mgに替えて触媒(46)95mgを用いた以外は実施例1と同様の方法により、燃料電池用電極(46)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Capacity A fuel cell electrode (46) was prepared in the same manner as in Example 1 except that 95 mg of catalyst (46) was used instead of 95 mg of catalyst (1), The oxygen reduction ability was evaluated.
1.触媒の製造
チタンテトライソプロポキシド(純正化学(株)製)9.37gおよびアセチルアセトン(純正化学)5.12gを、エタノール15mLおよび酢酸5mLの混合液に加え、室温で攪拌しながらチタン溶液を調製した。また、エチレングリコール8.30gおよび酢酸鉄(Aldrich社製)0.582gを純水20mLに加え、室温で攪拌して完全に溶解させてエチレングリコール溶液を調製した。チタン溶液をエチレングリコール溶液にゆっくり添加し、透明な触媒前駆体溶液を得た。ロータリーエバポレーターを用い、窒素雰囲気の減圧下で、ホットスターラーの温度を約100℃に設定し、前記触媒前駆体溶液を加熱かつ攪拌しながら、溶媒をゆっくり蒸発させた。完全に溶媒を蒸発させて得られた固形分残渣を乳鉢で細かく均一に潰して、焼成用粉末を得た。 [Comparative Example 1]
1. Production of catalyst Titanium tetraisopropoxide (manufactured by Junsei Chemical Co., Ltd.) 9.37 g and acetylacetone (Junsei Kagaku) 5.12 g are added to a mixture of
触媒(1)0.095gに替えて触媒(c1)0.095gを用いた以外は実施例1と同様の方法により、燃料電池用電極(c1)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reducing Ability Fuel Cell Electrode (c1) by the same method as in Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
1.触媒の製造
エチレングリコールに替えてシュウ酸12.05gを用いた以外は比較例1と同様の操作を行い、粉末状の触媒(c2)を得た。 [Comparative Example 2]
1. Production of catalyst A powdery catalyst (c2) was obtained in the same manner as in Comparative Example 1, except that 12.05 g of oxalic acid was used instead of ethylene glycol.
触媒(1)0.095gに替えて触媒(c2)0.095gを用いた以外は実施例1と同様の方法により、燃料電池用電極(c2)を作製し、その酸素還元能を評価した。 2. Production of electrode for fuel cell and evaluation of oxygen reduction ability Electrode for fuel cell (c2) by the same method as Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
1.触媒の製造
エチレングリコールに替えてグリコール酸10.18gを用いた以外は比較例1と同様の操作を行い、粉末状の触媒(c3)を得た。 [Comparative Example 3]
1. Production of catalyst A powdery catalyst (c3) was obtained in the same manner as in Comparative Example 1, except that 10.18 g of glycolic acid was used instead of ethylene glycol.
触媒(1)0.095gに替えて触媒(c3)0.095gを用いた以外は実施例1と同様の方法により、燃料電池用電極(c3)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reduction Capability Fuel Cell Electrode (c3) By the same method as in Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
1.触媒の製造
酸化チタン(アナターゼ型、100m2/g)を管状炉に入れ、水素ガスを4体積%含む窒素ガスの雰囲気下で昇温速度10℃/minで900℃まで加熱し、900℃で1時間保持し、自然冷却することにより粉末状の触媒(c4)を得た。 [Comparative Example 4]
1. Production of catalyst Titanium oxide (anatase type, 100 m 2 / g) was put in a tubular furnace, heated to 900 ° C. at a temperature rising rate of 10 ° C./min in an atmosphere of nitrogen gas containing 4% by volume of hydrogen gas, and at 900 ° C. The powdery catalyst (c4) was obtained by holding for 1 hour and naturally cooling.
触媒(1)0.095gに替えて触媒(c4)0.095gを用いた以外は実施例1と同様の方法により、燃料電池用電極(c4)を作製し、その酸素還元能を評価した。 2. Production of electrode for fuel cell and evaluation of oxygen reduction ability Electrode for fuel cell (c4) by the same method as in Example 1 except that 0.095 g of catalyst (c4) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
1.触媒の製造
酸化チタン(アナターゼ型、100m2/g)2gとカーボンブラック(キャボット社製 VULCAN(登録商標) XC72)0.75gを乳鉢中でよく混合し、管状炉に入れ、水素ガスを4体積%含む窒素ガスの雰囲気下で昇温速度10℃/minで1700℃まで加熱し、1700℃で3時間保持し、自然冷却することにより粉末状の触媒(c5)を得た。 [Comparative Example 5]
1. Production of catalyst 2 g of titanium oxide (anatase type, 100 m 2 / g) and 0.75 g of carbon black (VULCAN (registered trademark) XC72) manufactured by Cabot Corporation were mixed well in a mortar, placed in a tubular furnace, and 4 volumes of hydrogen gas were added. In a nitrogen gas atmosphere containing 1%, the catalyst was heated to 1700 ° C. at a temperature rising rate of 10 ° C./min, held at 1700 ° C. for 3 hours, and naturally cooled to obtain a powdery catalyst (c5).
触媒(1)0.095gに替えて触媒(c5)0.095gを用いた以外は実施例1と同様の方法により、燃料電池用電極(c5)を作製し、その酸素還元能を評価した。 2. Production of Fuel Cell Electrode and Evaluation of Oxygen Reduction Capacity Fuel Cell Electrode (c5) By the same method as in Example 1 except that 0.095 g of catalyst (1) was used instead of 0.095 g of catalyst (1) Were prepared and their oxygen reducing ability was evaluated.
Claims (16)
- 少なくとも金属化合物(1)と、窒素含有有機化合物(2)と、溶媒とを混合して触媒前駆体溶液を得る工程(1)、
前記触媒前駆体溶液から溶媒を除去する工程(2)、および
工程(2)で得られた固形分残渣を500~1100℃の温度で熱処理して電極触媒を得る工程(3)
を含み、
前記金属化合物(1)の一部または全部が、金属元素としてアルミニウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、ストロンチウム、イットリウム、スズ、タングステンおよびセリウムから選ばれる金属元素M1を含有する化合物であり、
前記工程(1)で用いられる成分のうち溶媒以外の少なくとも1つの成分が酸素原子を有する
ことを特徴とする燃料電池用電極触媒の製造方法。 A step (1) of obtaining a catalyst precursor solution by mixing at least a metal compound (1), a nitrogen-containing organic compound (2), and a solvent;
Step (2) for removing the solvent from the catalyst precursor solution, and Step (3) for obtaining an electrode catalyst by heat-treating the solid residue obtained in Step (2) at a temperature of 500 to 1100 ° C.
Including
A part or all of the metal compound (1) is a compound containing a metal element M1 selected from aluminum, chromium, manganese, iron, cobalt, nickel, copper, strontium, yttrium, tin, tungsten and cerium as a metal element. Yes,
A method for producing an electrode catalyst for a fuel cell, wherein at least one component other than the solvent among the components used in the step (1) has an oxygen atom. - 前記工程(1)において、ホウ素、リンおよび硫黄からなる群から選ばれる少なくとも1種の元素Aならびにフッ素を含有する化合物(3)をさらに混合することを特徴とする請求項1に記載の燃料電池用電極触媒の製造方法。 2. The fuel cell according to claim 1, wherein in the step (1), at least one element A selected from the group consisting of boron, phosphorus and sulfur and a compound (3) containing fluorine are further mixed. For producing an electrode catalyst.
- 前記化合物(3)が、フッ素を含有するホウ酸誘導体、フッ素を含有するスルホン酸誘導体およびフッ素を含有するリン酸誘導体からなる群から選ばれる少なくとも1種であることを特徴とする請求項2に記載の燃料電池用電極触媒の製造方法。 The compound (3) is at least one selected from the group consisting of a boric acid derivative containing fluorine, a sulfonic acid derivative containing fluorine, and a phosphoric acid derivative containing fluorine. The manufacturing method of the electrode catalyst for fuel cells of description.
- 前記工程(1)において、前記金属化合物(1)の溶液と、前記窒素含有有機化合物(2)とを混合することを特徴とする請求項1~3のいずれかに記載の燃料電池用電極触媒の製造方法。 The fuel cell electrode catalyst according to any one of claims 1 to 3, wherein, in the step (1), the solution of the metal compound (1) and the nitrogen-containing organic compound (2) are mixed. Manufacturing method.
- 前記工程(1)において、ジケトン構造を有する化合物からなる沈殿抑制剤をさらに混合することを特徴とする請求項1~4のいずれかに記載の燃料電池用電極触媒の製造方法。 The method for producing an electrode catalyst for a fuel cell according to any one of claims 1 to 4, wherein in the step (1), a precipitation inhibitor comprising a compound having a diketone structure is further mixed.
- 前記金属化合物(1)が、金属リン酸塩、金属硫酸塩、金属硝酸塩、金属有機酸塩、金属酸ハロゲン化物、金属アルコキシド、金属ハロゲン化物、金属過ハロゲン酸塩、金属次亜ハロゲン酸塩および金属錯体からなる群から選ばれる少なくとも1種であることを特徴とする請求項1~5のいずれかに記載の燃料電池用電極触媒の製造方法。 The metal compound (1) is a metal phosphate, metal sulfate, metal nitrate, metal organic acid salt, metal acid halide, metal alkoxide, metal halide, metal perhalogenate, metal hypohalite and 6. The method for producing an electrode catalyst for a fuel cell according to claim 1, wherein the method is at least one selected from the group consisting of metal complexes.
- 前記窒素含有有機化合物(2)が、アミノ基、ニトリル基、イミド基、イミン基、ニトロ基、アミド基、アジド基、アジリジン基、アゾ基、イソシアネート基、イソチオシアネート基、オキシム基、ジアゾ基、およびニトロソ基、ならびにピロール環、ポルフィリン環、イミダゾール環、ピリジン環、ピリミジン環、およびピラジン環から選ばれる1種類以上を分子中に有することを特徴とする請求項1~6のいずれかに記載の燃料電池用電極触媒の製造方法。 The nitrogen-containing organic compound (2) is an amino group, nitrile group, imide group, imine group, nitro group, amide group, azide group, aziridine group, azo group, isocyanate group, isothiocyanate group, oxime group, diazo group, And nitroso group, and one or more kinds selected from a pyrrole ring, porphyrin ring, imidazole ring, pyridine ring, pyrimidine ring, and pyrazine ring in the molecule. A method for producing an electrode catalyst for a fuel cell.
- 前記窒素含有有機化合物(2)が、水酸基、カルボキシル基、アルデヒド基、酸ハライド基、スルホ基、リン酸基、ケトン基、エーテル基、およびエステル基から選ばれる1種類以上を分子中に有することを特徴とする請求項1~7のいずれかに記載の燃料電池用電極触媒の製造方法。 The nitrogen-containing organic compound (2) has one or more kinds selected from a hydroxyl group, a carboxyl group, an aldehyde group, an acid halide group, a sulfo group, a phosphoric acid group, a ketone group, an ether group, and an ester group in the molecule. The method for producing an electrode catalyst for a fuel cell according to any one of claims 1 to 7, wherein:
- 前記工程(3)において、前記固形分残渣を、水素ガスを0.01体積%以上10体積%以下含む雰囲気中で熱処理することを特徴とする請求項1~8のいずれかに記載の燃料電池用電極触媒の製造方法。 9. The fuel cell according to claim 1, wherein, in the step (3), the solid residue is heat-treated in an atmosphere containing 0.01% by volume to 10% by volume of hydrogen gas. For producing an electrode catalyst.
- 請求項1~9のいずれかに記載の製造方法で得られる燃料電池用電極触媒。 A fuel cell electrode catalyst obtained by the production method according to any one of claims 1 to 9.
- 請求項10に記載の燃料電池用電極触媒を含むことを特徴とする燃料電池用触媒層。 A fuel cell catalyst layer comprising the fuel cell electrode catalyst according to claim 10.
- 請求項11に記載の燃料電池用触媒層と多孔質支持層とを有することを特徴とする電極。 An electrode comprising the fuel cell catalyst layer according to claim 11 and a porous support layer.
- カソードとアノードと前記カソードおよび前記アノードの間に配置された電解質膜とを有する膜電極接合体であって、前記カソードおよび/または前記アノードが請求項12に記載の電極であることを特徴とする膜電極接合体。 13. A membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is an electrode according to claim 12. Membrane electrode assembly.
- 請求項13に記載の膜電極接合体を備えることを特徴とする燃料電池。 A fuel cell comprising the membrane electrode assembly according to claim 13.
- 固体高分子型燃料電池であることを特徴とする請求項14に記載の燃料電池。 15. The fuel cell according to claim 14, which is a polymer electrolyte fuel cell.
- 発電機能、発光機能、発熱機能、音響発生機能、運動機能、表示機能および充電機能からなる群より選ばれる少なくとも一つの機能を有する物品であって、請求項14または15に記載の燃料電池を備えることを特徴とする物品。 16. An article having at least one function selected from the group consisting of a power generation function, a light emission function, a heat generation function, a sound generation function, an exercise function, a display function, and a charging function, comprising the fuel cell according to claim 14 or 15. Article characterized by that.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180064725.1A CN103299464B (en) | 2011-01-14 | 2011-08-09 | The manufacture method of electrode catalyst for fuel cell, electrode catalyst for fuel cell and its purposes |
JP2012532175A JP5108168B2 (en) | 2011-01-14 | 2011-08-09 | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof |
US13/979,305 US9350025B2 (en) | 2011-01-14 | 2011-08-09 | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and uses thereof |
EP11855699.2A EP2665119B1 (en) | 2011-01-14 | 2011-08-09 | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and uses thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-006191 | 2011-01-14 | ||
JP2011006191 | 2011-01-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012096023A1 true WO2012096023A1 (en) | 2012-07-19 |
Family
ID=46506942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/068184 WO2012096023A1 (en) | 2011-01-14 | 2011-08-09 | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and application thereof |
Country Status (5)
Country | Link |
---|---|
US (1) | US9350025B2 (en) |
EP (1) | EP2665119B1 (en) |
JP (3) | JP5108168B2 (en) |
CN (2) | CN103299464B (en) |
WO (1) | WO2012096023A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140162149A1 (en) * | 2012-12-10 | 2014-06-12 | Toto Ltd. | Solid oxide fuel cell |
WO2014208740A1 (en) * | 2013-06-28 | 2014-12-31 | 富士フイルム株式会社 | Method for producing nitrogen-containing carbon alloy, nitrogen-containing carbon alloy and fuel cell catalyst |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8709964B2 (en) * | 2010-09-14 | 2014-04-29 | Basf Se | Process for producing a carbon-comprising support |
JP5325355B2 (en) | 2011-08-09 | 2013-10-23 | 昭和電工株式会社 | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof |
CN104979568A (en) * | 2015-05-12 | 2015-10-14 | 北京化工大学 | Fuel cell cathode catalyst and preparation method thereof |
CN106025301B (en) * | 2016-07-01 | 2019-03-29 | 西北师范大学 | A kind of preparation and application of carried metal organic frame compound nitrogen functional carbon material |
WO2018026682A1 (en) * | 2016-08-02 | 2018-02-08 | Ballard Power Systems Inc. | Membrane electrode assembly with improved electrode |
CN109304195B (en) * | 2017-07-28 | 2022-04-08 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and application thereof |
CN110523970B (en) * | 2018-05-24 | 2022-04-08 | 中国石油化工股份有限公司 | Carbon-coated nickel nanoparticle and preparation method thereof |
CN109867300A (en) * | 2019-03-08 | 2019-06-11 | 桂林理工大学 | A kind of polymer assistant depositing preparation method of high-purity mayenite material |
CN110165180A (en) * | 2019-05-27 | 2019-08-23 | 华南理工大学 | A kind of rodlike nickel-cobalt-manganternary ternary anode material and preparation method thereof |
CN110231372B (en) * | 2019-07-17 | 2021-08-03 | 上海海事大学 | Gas sensor for acetone detection and preparation method thereof |
CN110783580B (en) * | 2019-11-15 | 2022-11-15 | 太原理工大学 | Preparation method of alkaline system fuel cell anode catalyst |
CN111883788A (en) * | 2020-06-24 | 2020-11-03 | 华南理工大学 | Preparation method of cerium oxide-based medium-low temperature solid oxide fuel cell key material |
CN114784304B (en) * | 2022-04-21 | 2024-04-02 | 佛山仙湖实验室 | Bimetallic atom doped porous carbon material catalyst and preparation method and application thereof |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324093A (en) * | 1994-05-31 | 1995-12-12 | Tanaka Kikinzoku Kogyo Kk | Production of tris(acetylacetonato)luthenium (iii) |
US20040096728A1 (en) | 2002-07-31 | 2004-05-20 | Ballard Power Systems Inc. | Non-noble metal catalysts for the oxygen reduction reaction |
JP2004303664A (en) | 2003-03-31 | 2004-10-28 | Japan Science & Technology Agency | Carbide electrode catalyst |
JP2005019332A (en) | 2003-06-27 | 2005-01-20 | Junichi Ozaki | Electrode catalyst for fuel cell, fuel cell using it, and electrode |
WO2006104123A1 (en) * | 2005-03-28 | 2006-10-05 | Stella Chemifa Corporation | Fuel cell |
WO2007072665A1 (en) | 2005-12-19 | 2007-06-28 | National University Corporation Yokohama National University | Oxygen reduction electrode for direct fuel cell |
JP2008021638A (en) * | 2006-06-16 | 2008-01-31 | Osaka City | Manufacturing method of iron-containing carbon material |
WO2008111570A1 (en) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | Membrane-electrode assembly and fuel cell using the membrane-electrode assembly |
JP2008258150A (en) | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Electrode catalyst for fuel cell |
WO2009028408A1 (en) * | 2007-08-29 | 2009-03-05 | Showa Denko K.K. | Electrode catalyst layer, membrane electrode assembly and fuel cell |
WO2009031383A1 (en) | 2007-09-07 | 2009-03-12 | Showa Denko K.K. | Catalyst, method for producing the same, and use of the same |
WO2009107518A1 (en) | 2008-02-28 | 2009-09-03 | 昭和電工株式会社 | Catalyst, method for producing the same, and use of the same |
WO2009124905A1 (en) * | 2008-04-07 | 2009-10-15 | Acta S.P.A. | High performance orr (oxygen reduction reaction) pgm (pt group metal) free catalyst |
JP2009255053A (en) | 2008-03-21 | 2009-11-05 | Sumitomo Chemical Co Ltd | Manufacturing method of electrode catalyst, and electrode catalyst |
WO2011099493A1 (en) * | 2010-02-10 | 2011-08-18 | 昭和電工株式会社 | Method of producing fuel cell electrode catalyst, method of producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses of same |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4061575B2 (en) * | 2001-06-01 | 2008-03-19 | ソニー株式会社 | Conductive catalyst particles and method for producing the same, gas diffusive catalyst electrode, and electrochemical device |
JP2007311026A (en) * | 2004-07-05 | 2007-11-29 | Gunma Univ | Electrode catalyst for fuel cell, its manufacturing method, and fuel cell using the catalyst |
JP4452887B2 (en) * | 2005-07-13 | 2010-04-21 | 国立大学法人群馬大学 | Method for producing electrode catalyst for fuel cell, electrode catalyst produced by the method, and fuel cell using the electrode catalyst |
JP4452889B2 (en) | 2006-02-03 | 2010-04-21 | 国立大学法人群馬大学 | ELECTRODE CATALYST FOR FUEL CELL, METHOD FOR PRODUCING THE SAME, AND FUEL CELL USING THE CATALYST |
WO2008111569A1 (en) | 2007-03-09 | 2008-09-18 | National Institute Of Advanced Industrial Science And Technology | Electrode catalyst for fuel cell |
JP2008258152A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Membrane-electrode assembly and fuel cell using this |
JP2009208061A (en) | 2008-02-06 | 2009-09-17 | Gunma Univ | Carbon catalyst, slurry containing the carbon catalyst, manufacturing method of carbon catalyst, fuel cell using carbon catalyst, electric storage device and environmental catalyst |
CN103700867B (en) * | 2008-03-24 | 2016-05-25 | 昭和电工株式会社 | Catalyst and manufacture method thereof with and uses thereof |
JP5481646B2 (en) | 2008-06-04 | 2014-04-23 | 清蔵 宮田 | Carbon catalyst, fuel cell, power storage device |
JP5320579B2 (en) | 2008-06-05 | 2013-10-23 | 清蔵 宮田 | Gas diffusion electrode and manufacturing method thereof, membrane electrode assembly and manufacturing method thereof, fuel cell member and manufacturing method thereof, fuel cell, power storage device and electrode material |
JP5375146B2 (en) | 2009-02-09 | 2013-12-25 | トヨタ自動車株式会社 | Method for producing supported catalyst for fuel cell |
WO2010107028A1 (en) | 2009-03-18 | 2010-09-23 | 昭和電工株式会社 | Catalyst for air battery, and air battery using same |
JP2010227843A (en) | 2009-03-27 | 2010-10-14 | Sumitomo Chemical Co Ltd | Method for producing electrode catalyst, and electrode catalyst |
JPWO2010131636A1 (en) | 2009-05-11 | 2012-11-01 | 昭和電工株式会社 | Catalyst, method for producing the same and use thereof |
CN103299465B (en) * | 2011-01-14 | 2015-09-16 | 昭和电工株式会社 | The manufacture method of electrode catalyst for fuel cell, electrode catalyst for fuel cell and its purposes |
EP2666541A4 (en) * | 2011-01-20 | 2014-07-02 | Showa Denko Kk | Catalyst carrier production method, composite catalyst production method, composite catalyst, fuel cell using same |
-
2011
- 2011-08-09 US US13/979,305 patent/US9350025B2/en active Active
- 2011-08-09 WO PCT/JP2011/068184 patent/WO2012096023A1/en active Application Filing
- 2011-08-09 JP JP2012532175A patent/JP5108168B2/en not_active Expired - Fee Related
- 2011-08-09 EP EP11855699.2A patent/EP2665119B1/en not_active Not-in-force
- 2011-08-09 CN CN201180064725.1A patent/CN103299464B/en not_active Expired - Fee Related
- 2011-08-09 CN CN201610048425.9A patent/CN105449228B/en not_active Expired - Fee Related
-
2012
- 2012-10-04 JP JP2012222082A patent/JP5805042B2/en not_active Expired - Fee Related
- 2012-10-04 JP JP2012222081A patent/JP5975826B2/en not_active Expired - Fee Related
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324093A (en) * | 1994-05-31 | 1995-12-12 | Tanaka Kikinzoku Kogyo Kk | Production of tris(acetylacetonato)luthenium (iii) |
US20040096728A1 (en) | 2002-07-31 | 2004-05-20 | Ballard Power Systems Inc. | Non-noble metal catalysts for the oxygen reduction reaction |
JP2004303664A (en) | 2003-03-31 | 2004-10-28 | Japan Science & Technology Agency | Carbide electrode catalyst |
JP2005019332A (en) | 2003-06-27 | 2005-01-20 | Junichi Ozaki | Electrode catalyst for fuel cell, fuel cell using it, and electrode |
WO2006104123A1 (en) * | 2005-03-28 | 2006-10-05 | Stella Chemifa Corporation | Fuel cell |
WO2007072665A1 (en) | 2005-12-19 | 2007-06-28 | National University Corporation Yokohama National University | Oxygen reduction electrode for direct fuel cell |
JP2008021638A (en) * | 2006-06-16 | 2008-01-31 | Osaka City | Manufacturing method of iron-containing carbon material |
WO2008111570A1 (en) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | Membrane-electrode assembly and fuel cell using the membrane-electrode assembly |
JP2008258150A (en) | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Electrode catalyst for fuel cell |
WO2009028408A1 (en) * | 2007-08-29 | 2009-03-05 | Showa Denko K.K. | Electrode catalyst layer, membrane electrode assembly and fuel cell |
WO2009031383A1 (en) | 2007-09-07 | 2009-03-12 | Showa Denko K.K. | Catalyst, method for producing the same, and use of the same |
WO2009107518A1 (en) | 2008-02-28 | 2009-09-03 | 昭和電工株式会社 | Catalyst, method for producing the same, and use of the same |
JP2009255053A (en) | 2008-03-21 | 2009-11-05 | Sumitomo Chemical Co Ltd | Manufacturing method of electrode catalyst, and electrode catalyst |
WO2009124905A1 (en) * | 2008-04-07 | 2009-10-15 | Acta S.P.A. | High performance orr (oxygen reduction reaction) pgm (pt group metal) free catalyst |
WO2011099493A1 (en) * | 2010-02-10 | 2011-08-18 | 昭和電工株式会社 | Method of producing fuel cell electrode catalyst, method of producing transition metal oxycarbonitride, fuel cell electrode catalyst, and uses of same |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140162149A1 (en) * | 2012-12-10 | 2014-06-12 | Toto Ltd. | Solid oxide fuel cell |
US9515322B2 (en) * | 2012-12-10 | 2016-12-06 | Toto Ltd. | Solid oxide fuel cell |
CN103872342B (en) * | 2012-12-10 | 2017-05-17 | Toto株式会社 | Solid oxide fuel cell |
WO2014208740A1 (en) * | 2013-06-28 | 2014-12-31 | 富士フイルム株式会社 | Method for producing nitrogen-containing carbon alloy, nitrogen-containing carbon alloy and fuel cell catalyst |
JP2015027934A (en) * | 2013-06-28 | 2015-02-12 | 富士フイルム株式会社 | Manufacturing method of nitrogen-containing carbon alloy, nitrogen-containing carbon alloy, and fuel cell catalyst |
Also Published As
Publication number | Publication date |
---|---|
EP2665119A1 (en) | 2013-11-20 |
JP5975826B2 (en) | 2016-08-23 |
JP5108168B2 (en) | 2012-12-26 |
US9350025B2 (en) | 2016-05-24 |
CN103299464A (en) | 2013-09-11 |
CN103299464B (en) | 2016-02-24 |
US20130295483A1 (en) | 2013-11-07 |
EP2665119A4 (en) | 2015-01-14 |
JP2013038083A (en) | 2013-02-21 |
JP2013048099A (en) | 2013-03-07 |
JP5805042B2 (en) | 2015-11-04 |
EP2665119B1 (en) | 2018-10-24 |
JPWO2012096023A1 (en) | 2014-06-09 |
CN105449228A (en) | 2016-03-30 |
CN105449228B (en) | 2018-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5975826B2 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof | |
JP5766138B2 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof | |
JP6061998B2 (en) | Electrocatalysts for fuel cells, transition metal carbonitrides and their uses | |
JP5325355B2 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof | |
JP5302468B2 (en) | Oxygen reduction catalyst, method for producing the same, and polymer electrolyte fuel cell | |
KR101618928B1 (en) | Method for manufacturing electrocatalyst for fuel cell and use thereof | |
JP5255160B1 (en) | Fuel cell electrode catalyst and method for producing the same | |
JP5837356B2 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof | |
JP5837355B2 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof | |
JP4944281B1 (en) | Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180064725.1 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012532175 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11855699 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13979305 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011855699 Country of ref document: EP |